Polycarbonate/polyolefin based resin compositions and their production processes and uses

ABSTRACT

This invention provides the following resin composition, method for producing the composition, resin slide material, organic solvent resist material and glass fiber reinforced composition obtained therefrom. A polycarbonate/polyolefin based resin composition exhibiting an improved polycarbonate/polyolefin compatibility prepared by melt kneadin (A) a polycarbonate resin; (B) a polyolefin resin; (C) a polyolefin resin that has been modified with at least one functional group selected from the group consisting of epoxy, carboxyl, and an acid anhydride groups; (D) a compound represented by the formula: HOOC--R--NH 2  wherein R represents at least one member selected from the group consisting of an alkene group, an alkylidene group, and an oligomethylene group containing 5 or more carbon atoms, and phenylene group and naphthylene group optionally substituted with an alkyl group; and optionally, (E) a styrene copolymer resin.

CROSS-REFERENCE TO RELATED APPLICATIONS

This is a division of application Ser. No. 08/402,688, filed Mar. 13,1995, now U.S. Pat. No. 5,594,062.

BACKGROUND OF THE INVENTION

First of all, this invention relates to a resin composition comprising apolycarbonate and a polyolefin which exhibits an improvedpolycarbonate/polyolefin compatibility and improved delaminationresistance and which also has sufficient mechanical strength and heatresistance. This invention also relates to a method for producing suchresin composition. In the second place, this invention relates to resincompositions comprising a polycarbonate and a polyolefin which haveimproved wear resistant properties or an improved solvent resistance,and articles produced by melt molding such resin compositions. In thethird place, this invention relates to compositions wherein theabove-described resin compositions are further blended with glass fiber,and articles molded from such compositions. The materials provided bythe present invention are particularly preferable for use in officeautomation equipment, household appliance, automobile components,medical instruments, and the like.

Polycarbonate resins have been widely used in the field of automobilesand electricity owing to their excellent heat resistance, impactresistance, and electric properties as well as good dimensionalstability. Polycarbonate resins, however, suffer from high meltviscosity and poor organic solvent resistance as well as poorabrasion/friction properties, and their use was limited in the fieldswherein such properties were required. In order to obviate such defectsof the polycarbonates, various attempts have been suggested wherein thepolycarbonate is mixed with a polyolefin (See for example, JapanesePatent Publication No. 40(1965)-13664 and Japanese Patent ApplicationLaid-Open No. 59(1984)-22371-). Such resin compositions, however, failedto prove practical since the low compatibility of the polycarbonate andthe polyolefin resulted in delamination, and hence, in poor appearanceof the produce when a molded article is produced from the resincomposition by such means as injection molding. Various attempts havebeen made to improve the compatibility of the polycarbonate and thepolyolefin by incorporating into the polycarbonate-polyolefin resincomposition a polystyrene-polyolefin copolymer such as SEBS(styrene-ethylene/butylene-styrene copolymer), SEP(styrene-ethylene/propylene), or the like (See for example, JapanesePatent Application Laid-Open No. 64(1989)-75543). However, theincorporated polystyrene-polyolefin copolymer is of elastomeric nature,and the resulting resin composition suffered particularly from poor heatresistance and flexural rigidity.

Japanese Patent Application Laid-Open No. 63(1988)-215750 discloses aresin composition wherein the polycarbonate-polyolefin resin furthercomprises a polycarbonate having a terminal carboxyl group and apolypropylene having epoxy group; and Japanese Patent ApplicationLaid-Open No. 63(1988)-215752 discloses a resin composition wherein thepolycarbonate-polyolefin resin further comprises a polycarbonate havinga terminal hydroxyl group and polypropylene having carboxyl group. Suchcompositions do not undergo delamination, and the articles prepared fromsuch compositions exhibit excellent mechanical strength and organicsolvent resistance as well as improved outer appearance with nodelamination. However, the carboxyl- and the hydroxyl-containingpolycarbonates used or constituting such resins are those respetivelyprepared by adding a special monomer in the polymerization stage of thepolycarbonate resin, and production of such resins would require apolycarbonate polymerization installation. Therefore, processesutilizing such components would out a heavy financial burden to resinmanufacturers that do not have such polycarbonate polymerizationinstallation. Accordingly, production of the polycarbonate-polyolefinresin further comprising such resin component was rather difficult. Inaddition, the properties of the resin composition estimated from thevalue described in the disclosed specification are not fully sufficientin view of the properties inherent to the polycarbonate, and furtherimprovements in the properties are desired.

Attempts have also been made to add a fluororesin such aspolytetrafluoroethylene to the polycarbonate resin to thereby improvefriction/abrasion properties. Such composition has improved wearresistant properties in addition to the above-described excellentproperties inherent to the polycarbonate resin, and therefore, suchcomposition is used for such parts as gears and cums of officeautomation equipment and household appliance where heat resistance,impact strength, and wear resistant properties are required. However,the fluororesin used in such composition is rather expensive, and uponthermal disposal of the resin composition, the fluororesin wouldgenerate toxic gases. In view of such situation, there has been a strongdemand for a polycarbonate based resin slide material that maysubstitute for the polycarbonate/fluororesin based resin composition.

On the other hand, polyolefin resins, and in particular, high densitypolyethylene, low density polyethylene, and straight-chain low densitypolyethylene are inexpensive and excellent in friction/abrasionproperties. Such polyolefin resins are, however, inferior to thepolycarbonate resins in their heat resistance, flexural rigidity, andflame retardancy. Therefore, it has been difficult to use the polyolefinresin in the applications where the polycarbonate/fluororesin basedresin composition had been used. In view of such situation, variousattempts have been made to mix the polycarbonate with the polyethylenein order to develop a resin composition which is provided with both theexcellent heat resistance, Impact resistance, and flame retardancy ofthe polycarbonate resin and the excellent friction/abrasion propertiesof the polyethylene. In spite of such attempts, the markedly poorcompatibility of the polycarbonate with the polyethylene resulted indelamination of the molded article, especially upon frictional contactor under abrasion, leading to poor abrasion properties. Accordingly, themixing of the polycarbonate and the polyethylene by simple kneadingproved insufficient.

Polycarbonate resins are amorphous, and suffer from cracks when they arebrought in contact with an organic solvent for a prolonged period. Suchcracks result in significantly poor appearance and markedly reducedmechanical strength. Therefore, use of the polycarbonate resins waslimited in applications where organic resistance was required. In viewof such situation, attempts have been made to combine the polycarbonatewith a crystalline polyester such as polyethylene terehthalate andpolybutylene terephthalate to thereby improve the organic solventresistance of the polycarbonate. Such compositions exhibit goodcompatibility and well balanced mechanical strength and organic solventresistance. However, the polyethylene terephthalate and the polybutyleneterephthalate used in such resins are rather expensive. Althoughpolyolefins such as polypropylene and polyethylene are excellent inorganic solvent resistance and more inexpensive than such polyesters,polyolefins suffer from poor compatibility with the polycarbonate. Asdescribed above, mixing of the polycarbonate and the polyolefin bysimple kneading failed to provide the molded article whose organicsolvent resistance and appearance (resistance to delamination) werefully improved, Accordingly, no means are so far available that canimprove the solvent resistance of the polycarbonate resin in aninexpensive manner.

Glass fiber-reinforced polycarbonate resins comprising a polycarbonateresin and glass fibers blended therewith have improved flexuralrigidity, heat resistance and abrasion properties compared to the resincomposition solely comprising the polycarbonate resin. The glassfiber-reinforced polycarbonate resins, however, are still insufficientin abrasion properties, and accordingly, use of such resins was limitedin the applications where friction/abrasion properties are required, forexample, gear, cum, and bearing.

In view of such situation, attempts have been made to combine the glassfiber-reinforced polycarbonate resins with a fluororesin such aspolytetrafluoroethylene to thereby improve the friction/abrasionproperties. Such resin compositions having the fluororesin incorporatedtherein have improved wear resistant properties in addition to theabove-described excellent properties inherent to the polycarbonateresin, and therefore, such compositions are used for such parts as gearsand cums of office automation equipment and household appliance whereheat resistance, impact strength, flexural rigidity, and wear resistantproperties are required However, the fluororesin used in suchcomposition suffer from the disadvantages as described above, and thereis a strong demand for a polycarbonate based resin slide material thatcan substitute for the glass fiber-reinforced polycarbonate/fluororesinbased resin compositions.

On the other hand, polyolefin resins, and in particular, high densitypolyethylene, low density polyethylene, and straight-chain low densitypolyethylene are inexpensive and excellent in friction/abrasionproperties, as described above. However, the polyolefin resins havingglass fibers admixed therewith are inferior to the glassfiber-reinforced polycarbonate resins in their heat resistance, flexuralrigidity, and flame retardancy. Therefore, it has been difficult to usethe glass fiber-reinforced polyolefin resin in the applications wherethe glass fiber-reinforced polycarbonate/fluororesin based resincompositions had been used.

In view of such situation, various attempts have been made toincorporate the glass fiber into the mixture of the polycarbonate withthe polyethylene in order to develop a glass fiber-reinforcedpolycarbonate based resin composition which is provided with both theexcellent heat resistance, impact resistance, and flame retardancy ofthe polycarbonate resin and the excellent friction/abrasion propertiesof the polyethylene. As described above, the compatibility of thepolycarbonate with the polyethylene is quite poor, and the articlemolded from the resin composition prepared by simple kneading of thecomponents suffered from delamination, especially upon frictionalcontact or under abrasion, leading to poor abrasion properties. Suchsituation is not at all improved by mere incorporation of the glassfiber into the resin composition.

First object of the present invention is to provide apolycarbonate/polyolefin based resin composition which is provided withthe excellent mechanical properties of the polycarbonate and theexcellent molding properties of the polyolefin, and which is excellentin surface properties without suffering from delamination; and to enablethe production of such polycarbonate/polyolefin based resin compositionby blending readily available starting materials in a convenient manner.

Second object of the present invention is to provide a method forproducing such polycarbonate/polyolefin based resin composition whereina simple kneading machine may be utilized in the production.

Third object of the present invention is to provide an inexpensive resinslide material with excellent heat resistance, mechanical properties,and flame retardancy as well as sufficient wear resistant properties;and more illustratively, to provide a polycarbonate/polyolefin basedresin composition exhibiting an improved polycarbonate/polyolefincompatibility and improved wear resistant properties as well as a moldedarticle produced by melt molding such resin composition.

Fourth object of the present invention is to provide an inexpensivepolycarbonate/polyolefin based resin composition with excellent heatresistance, mechanical properties, and flame retardancy as well assufficient organic solvent resistance which exhibits improvedpolycarbonate/polyolefin compatibility; and a molded material producedby melt molding such resin composition.

Fifth object of the present invention is to provide an inexpensive glassfiber-reinforced polycarbonate/polyolefin based resin composition withexcellent heat resistance, mechanical properties, and flame retardancyas well as sufficient wear resistant properties which exhibits improvedpolycarbonate/polyolefin compatibility; and to provide a molded articlewith excellent heat resistance, mechanical properties, and flameretardancy as well as sufficient wear resistant properties fabricatedfrom such glass fiber-reinforced polycarbonate-polyolefin based resincomposition.

SUMMARY OF THE INVENTION

According to the present invention, there is provided a precursor of acompatibilizer for a polycarbonate resin and a polyolefin resin preparedby reacting

(C) a polyolefin resin that has been modified with at least onefunctional group selected from the group consisting of epoxy, carboxyl,and an acid anhydride groups; and

(D) a compound represented by the formula: HOOC--R--NH₂ wherein Rrepresents at least one member selected from the group consisting of analkene group, an alkylidene group, and an oligomethylene groupcontaining 5 or more carbon atoms, and phenylene group and naphthylenegroup optionally substituted with an alkyl group.

According to the present invention, there is also provided acompatibilizer for a polycarbonate resin and a polyolefin resin preparedby reacting

(A) a polycarbonate resin;

(C) a polyolefin resin that has been modified with at least onefunctional group selected from the group consisting of epoxy, carboxyl,and an acid anhydride groups; and

(D) a compound represented by the formula: HOOC--R--NH₂ wherein Rrepresents at least one member selected from the group consisting of analkene group, an alkylidene group, and an oligomethylene groupcontaining 5 or more carbon atoms, and phenylene group and naphthylenegroup optionally substituted with an alkyl group.

Furthermore, there is provided according to the present invention apolycarbonate/polyolefin based resin composition exhibiting an improvedpolycarbonate/polyolefin compatibility prepared by melt kneading

(A) a polycarbonate resin;

(C) a polyolefin resin that has been modified with at least onefunctional group selected from the group consisting of epoxy, carboxyl,and an acid anhydride groups; and

(D) a compound represented by the formula: HOOC--R--NH₂ wherein Rrepresents at least one member selected from the group consisting of analkene group, an alkylidene group, and an oligomethylene groupcontaining 5 or more carbon atoms, and phenylene group and naphthylenegroup optionally substituted with an alkyl group.

Still further, there is provided according to the present invention apolycarbonate/polyolefin based resin composition exhibiting an improvedpolycarbonate/polyolefin compatibility prepared by melt kneading

(A) a polycarbonate resin;

(B) a polyolefin resin;

(C) a polyolefin resin that has been modified with at least onefunctional group selected from the group consisting of epoxy, carboxyl,and an acid anhydride groups; and

(D) a compound represented by the formula: HOOC--R--NH₂ wherein Rrepresents at least one member selected from the group consisting of analkene group, an alkylidene group, and an oligomethylene groupcontaining 5 or more carbon atoms, and phenylene group and naphthalenegroup optionally substituted with an alkyl group.

Still further, there is provided according to the present invention apolycarbonate/polyolefin based resin composition exhibiting an improvedpolycarbonate/polyolefin compatibility prepared by melt kneading

(A) a polycarbonate resin;

(B) a polyolefin resin;

(C) a polyolefin resin that has been modified with at least onefunctional group selected from the group consisting of epoxy, carboxyl,and an acid anhydride groups;

(D) a compound represented by the formula: HOOC--R--NH₂ wherein Rrepresents at least one member selected from, the group consisting of analkene group, an alkylidene group, and an oligomethylene groupcontaining 5 or more carbon atoms, and phenylene group and naphthylenegroup optionally substituted with an alkyl group; and

(E) a styrene copolymer resin.

Still further, there is provided according to the present invention apolycarbonate/polyolefin based resin composition exhibiting an improvedpolycarbonate/polyolefin compatibility wherein

40 to 99% by weight of the component (A);

60 to 0% by weight of the component (B);

0.5 to 60% by weight of the component (C); and

0.05 to 5% by weight of the component (D)

are melt kneaded.

Still further, there is provided according to the present invention apolycarbonate/polyolefin based resin composition exhibiting an improvedpolycarbonate/polyolefin compatibility wherein

40 to 99% by weight of the component (A);

60 to 0% by weight of the component (B);

0.5 to 60% by weight so the component (C);

0.05 to 5% by weight so the component (D); and

0.1 to 30% by weight of the component (E)

are melt kneaded.

Still further, there is provided according to the present invention apolycarbonate/polyolefin based resin composition exhibiting an improvedpolycarbonate/polyolefin compatibility wherein

1 to 99% by weight of the component (A);

98 to 0% by weight of the component (B);

0.5 to 99% by weight of the component (C); and

0.05 to 5% by weight of the component (D)

are melt kneaded.

Still further, there is provided according to the present invention apolycarbonate/polyolefin based resin composition exhibiting an improvedpolycarbonate/polyolefin compatibility wherein

1 to 99% by weight of component (A)

98 to 0% by weight of component (B);

0.5 to 99% by weight of component (C);

0.05 to 5% by weight of component (D); and

0.1 to 30% by weight of component (E)

are melt kneaded.

Still further, there is provided according to the present invention apolycarbonate/polyolefin based resin composition wherein the polyolefinin said modified polyolefin (C) is at least one member selected from thegroup consisting of polyethylene and polypropylene.

Still further, there is provided according to the present invention apolycarbonate/polyolefin based resin composition wherein the modifiedpolyolefin (C) is at least one member selected from the group consistingof maleic anhydride-modified Linear low density polyethylene, maleicanhydride-modified low density polyethylene, and maleicanhydride-modified high density polyethylene.

Still further, there is provided according to the present invention amolded article produced by melt molding the resin composition.

Still further, there is provided according to the present invention amolded article wherein the polyolefin is dispersed in the polycarbonatein particulate form, and the particulate polyolefin present in theregion from surface of the article to a depth of 20 μm has an averageaspect ratio (major axis/minor axis) of up to 5.

Still further, there is provided according to the present invention aglass fiber-reinforced resin composition comprising

95 to 60% by weight of the polycarbonate/polyolefin based resincomposition; and

5 to 40% by weight of glass fibers.

Still further, there is provided according to the present invention amolded article produced by melt molding the glass fiber-reinforced resincomposition.

Still further, there is provided according to the present invention amolded material having an improved solvent resistance comprising themolded article.

Still further, there is provided according to the present invention amolded material having improved wear resistant properties comprising themolded article.

Still further, there is provided according to the present invention aprocess for producing the resin composition comprising the step of meltkneading the compatibilizer precursor with the polycarbonate resin (A).

Still further, there is provided according to the present invention aprocess for producing the resin composition comprising the step of meltkneading the compatibilizer precursor with the polycarbonate resin (A),the polyolefin resin (B) and the styrene copolymer resin (E)simultaneously or sequentially in an arbitrary order.

Still further, there is provided according to the present invention aprocess for producing the resin composition comprising the step of meltkneading the compatibilizer with the polycarbonate resin (A).

Still further, there is provided according to the present invention aprocess for producing the resin composition comprising the step of meltkneading the compatibilizer with the polycarbonate resin (A), thepolyolefin resin (B) and the styrene copolymer resin (E) simultaneouslyor sequentially in an arbitrary order.

Still further, there is provided according to the present invention aprocess for producing the resin composition comprising the steps of

melt kneading the polyolefin resin (B), an acid anhydride, and thecompound (D) represented by the formula: HOOC--R--NH₂ wherein Rrepresents at least one member selected from the group consisting of analkene group, an alkylidene group, and an oligomethylene groupcontaining 5 or more carbon atoms, and phenylene group and naphthylenegroup optionally substituted with an alkyl group; and

continuing the melt kneading after adding the polycarbonate resin (A)and the styrene copolymer resin (E) simultaneously or sequentially in anarbitrary order.

Still further, there is provided according to the present invention aprocess or producing the resin composition comprising the steps of

melt kneading the polycarbonate resin (A) and the compound (D)represented by the formula: HOOC--R--NH₂ wherein R represents at leastone member selected from the group consisting of an alkene group, analkylidene group, and an oligomethylene group containing 5 or morecarbon atoms, and phenylene group and naphthylene group optionallysubstituted with an alkyl group; and

continuing the melt kneading after adding at least one componentselected from the group consisting of the polycarbonate resin (A), thepolyolefin resin (B), and the polyolefin resin (C) that has beenmodified with at least one functional group selected from the groupconsisting of epoxy, carboxyl, and an acid anhydride groups in anarbitrary order.

Still further, there is provided according to the present invention aresin composition wherein the modified polyolefin resin (C) is thepolyolefin resin modified with at least one functional group selectedfrom the group consisting of carboxyl and an acid anhydride groups; andthe resin composition has been produced through reaction of the modifiedpolyolefin resin (C) with the compound (D) represented by the formula:HOOC--R--NH₂ wherein R represents at least one member selected from thegroup consisting of an alkene group, an alkylidene group, and anoligomethylene group containing 5 or more carbon atoms, and phenylenegroup and naphthylene group optionally substituted with an alkyl group,whereby a linkage represented by formula (H): ##STR1## is produced.

Still further, there is provided according to the present invention aresin composition wherein the modified polyolefin resin (C) is thepolyolefin resin modified with epoxy group; and the resin compositionhas been produced through reaction of the modified polyolefin resin (C)with the compound (D) represented by the formula: HOOC--R--NH₂ wherein Rrepresents at least one member selected from the group consisting of analkene group, an alkylidene group, and an oligomethylene groupcontaining 5 or more carbon atoms, and phenylene group and naphthylenegroup optionally substituted with an alkyl group, whereby a linkagerepresented by formula (J): ##STR2## is produced.

According to one embodiment of the present invention, there is provideda polycarbonate/polyolefin based resin composition comprising

40 to 99% by weight of polycarbonate resin (A);

60 to 0% by weight of polyolefin resin (B);

0.5 to 60% by weight of polyolefin resin (C) that has been modified withat least one functional group selected from the group consisting ofepoxy, carboxyl, and an acid anhydride groups; and

0.05 to 5% by weight of compound (D) represented by the formula:HOOC--R--NH₂ wherein R represents at least one member selected from thegroup consisting of an alkene group, an alkylidene group, and anoligomethylene group containing 5 or more carbon atoms, and phenylenegroup and naphthylene group optionally substituted with an alkyl group.

According to another embodiment of the present invention, there isprovided a process for producing such a polycarbonate/polyolefin basedresin composition by melt kneading the components (A) to (D).

According to a further embodiment of the present invention, there isprovided a polycarbonate/polyolefin based resin composition comprising

40 to 99% by weight of polycarbonate resin (A);

60 to 0% by weight of polyolefin resin (B);

0.5 to 60% by weight of polyolefin resin (C) that has been modified withat least one functional group selected from the group consisting ofepoxy, carboxyl, and an acid anhydride groups;

0.05 to 5% by weight of compound (D) represented by the formula:HOOC--R--NH₂ wherein R represents at least one member selected from thegroup consisting of an alkene group, an alkylidene group, and anoligomethylene group containing 5 or more carbon atoms, and phenylenegroup and naphthylene group optionally substituted with an alkyl group;and

0.1 to 30% by weight of styrene copolymer (E)

According to a further embodiment of the present invention, there isprovided a process for producing such a polycarbonate/polyolefin basedresin composition by melt kneading the components (A) to (E).

According to a still further embodiment of the present invention, thereis provided a process for producing a polycarbonate/polyolefin basedresin composition comprising the steps of

(1) reacting 100 parts by weight of a polyolefin resin that has beenmodified with at least one functional group selected from the groupconsisting of epoxy, carboxyl, and an acid anhydride groups with 0.05 to5% by weight of compound represented by the formula: HOOC--R--NH₂wherein R represents at least one member selected from the groupconsisting of an alkene group, an alkylidene group, and anoligomethylene group containing 5 or more carbon atoms, and optionallysubstituted phenylene and naphthylene groups in a melt kneading machineat a temperature in the range of from 180° to 340° C. to produce apolyolefin resin that has been modified with the compound represented bythe formula: HOOC--R--NH₂ ; and

(2) melt kneading 2 to 40 parts by weight of the modified polyolefinresin produced in step (1) with 60 to 99 parts by weight of apolycarbonate resin having a melt index of from 1 to 30 at a temperatureof from 220° to 340° C.

According to a still further embodiment of the present invention, thereis provided a process for producing a polycarbonate/polyolefin basedresin composition comprising the steps of

(1) reacting 100 parts by weight of a polyolefin resin that has beenmodified with at least one functional group selected from the groupconsisting of epoxy, carboxyl, and an acid anhydride groups with 0.05 to5by weight of compound represented by the formula: HOOC--R--NH₂ whereinR represents at least one member selected from The group consisting ofan alkene group, an alkylidene group, and an oligomethylene groupcontaining 5 or lore carbon atoms, and optionally substituted phenyleneand naphthylene groups in a melt kneading machine at a temperature inthe range of from 180° to 340° C. to produce a polyolefin resin that hasbeen modified with the compound represented by the formula: HOOC--R--NH₂; and

(2) melt kneading 2 to 40 parts by weight of the modified polyolefinresin produced in step (1) with more than 0 to 20 parts by weight of apolyolefin resin and 60 to 99 parts by weight of a polycarbonate resinhaving a melt index of from 1 to 30 at a temperature of from 220° to340° C.

According to a still further embodiment of the present invention, thereis provided a glass fiber-reinforced polycarbonate resin compositioncomprising

95 to 60 parts by weight of a polycarbonate resin composition producedby melt kneading

99 to 85 parts by weight of polycarbonate resin (A);

1 to 15 parts by weight or polyethylene resin (c) that has been modifiedwith at least one functional group selected from the group consisting ofan acid, an acid anhydride, and epoxy groups; and

0.005 to 2.0 parts by weight of compound (D) represented by the formula:HOOC--R--N₂ wherein R represents at least one member selected from thegroup consisting of an alkylidene group and an alkene group containing 5or more carbon atoms, and phenylene group and naphthylene group that areoptionally substituted with an alkyl group; and

5 to 40 parts by weight of glass fiber.

In this embodiment, the modified polyethylene is at least one memberselected from the group consisting of straight-chain low densitypolyethylene modified with maleic anhydride, low density polyethylenemodified with maleic anhydride, and high density polyethylene modifiedwith maleic anhydride.

According to a still further embodiment of the present invention, thereis provided a molded article produced by melt molding such glassfiber-reinforced polycarbonate resin composition.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is an electron microscope photograph of a particle structureshowing the dispersion of constituent components of a compositioncomprising PC (70 wt %) and polypropylene (30 wt %);

FIG. 2 is an electron microscope photograph of a particle structureshowing the dispersion of constituent components of a compositionobtained by adding 11-aminoundecanoic acid (1.8 wt % based on a mixtureof PC (70 wt %) and maleic anhydride-modified polypropylene (30 wt %) tothe mixture;

FIG. 3 is an electron microscope photograph of a particle structureshowing the dispersion of constituent components of a compositionobtained by adding 11-aminoundecanoic acid (1.8 wt % based on a mixtureof PC (70 wt %) and epoxy-modified polypropylene (30 wt %) to themixture;

FIG. 4 is an electron microscope photograph (with 3000 magnifications)of a particle structure showing the dispersion of constituents of acomposition obtained by Example 10 (70 wt % PC, 30 wt % modifiedpolypropyrene with 11-aminoundecanoic acid);

FIG. 5 is an electron microscope photograph (with 3000 magnifications)of a particle structure showing the dispersion of constituents of acomposition obtained by Comparative Example 11 (70 wt % PC, 30 wt %polypropyrene without 11-aminoundecanoic acid);

FIG. 6A and 6B are electron microscope photographs A and B oftransmission type showing morphology in the vicinities of the surfacesof the ring woldings of Example 24 and comparative Example 17;

FIG. 7 is a graph showing a variation in linear wear loss of each of thecompositions of the examples and the comparative examples and the knownPC/PTFE wear resistant material as a functin of time;

FIG. 8 is a graph showing an increase (%) in weight of the test piece(Example 36, Comparative Example 21) immersed in gasoline as a functionof time (minutes);

FIG. 9 is a graph showing an increase (%) in weight of the test piece(Example 37, Comparative Example 22) immersed in gasoline as a functionof time (minutes); and

FIG. 10A to 10F are photographs showing test piece surfaces (with 6.5magnifications) observed after immersion in gasoline for 1320 minutes ofthe test pieces of the compositions of the examples 36(10D) and 37(10F),the comparative examples 21(10C) and 22(107E), PC(10A) and PC/PET(10B).

DETAILED DESCRIPTION OF THE INVENTION

1! According to the first aspect of the present invention whereby theabove-described first object of the present invention is attained, thereis provided resin compositions of the following three embodiments.

The resin composition according to the first embodiment is:

a polycarbonate/polyolefin based resin composition exhibiting animproved polycarbonate/polyolefin compatibility prepared by meltkneading

(A) a polycarbonate resin;

(C) a polyolefin resin that has been modified with at least onefunctional group selected from the group consisting of epoxy, carboxyl,and an acid anhydride groups; and

(D) a compound represented by the formula: HOOC--R--NH₂ wherein Rrepresents at least one member selected from the group consisting of analkene group, an alkylidene group, and an oligomethylene groupcontaining 5 or more carbon atoms, and phenylene group and naphthylenegroup optionally substituted with an alkyl group.

The resin composition according to the second embodiment is:

a polycarbonate/polyolefin based resin composition exhibiting animproved polycarbonate/polyolefin compatibility prepared by meltkneading

(A) a polycarbonate resin;

(B) a polyolefin resin;

(C) a polyolefin resin that has been modified with at least onefunctional group selected from the group consisting of epoxy, carboxyl,and an acid anhydride groups; and

(D) a compound represented by the formula: HOOC--R--NH₂ wherein Rrepresents at least one member selected from the group consisting of analkene group, an alkylidene group, and an oligomethylene groupcontaining 5 or more carbon atoms, and phenylene group and naphthylenegroup optionally substituted with an alkyl group.

The resin composition according to the third embodiment is:

a polycarbonate/polyolefin based resin composition exhibiting animproved polycarbonate/polyolefin compatibility prepared by meltkneading

(A) a polycarbonate resin;

(B) a polyolefin resin;

(C) a polyolefin resin that has been modified with at least onefunctional group selected from the group consisting of epoxy, carboxyl,and an acid anhydride groups;

(D) a compound represented by the formula: HOOC--R--NH₂ wherein Brepresents at least one member selected from the group consisting of analkene group, an alkylidene group, and an oligomethylene groupcontaining 5 or more carbon atoms, and phenylene group and naphthylenegroup optionally substituted with an alkyl group; and

(E) a styrene copolymer resin.

1-3! Components (A) to (E) used for the starting materials in producingthe polycarbonate/polyolefin based resin compositions of the presentinvention are described below.

(A) Polycarbonate resin

The polycarbonate resin which may be used in the present invention is athermoplastic aromatic polycarbonate polymer produced by reacting anaromatic hydroxy compound and an optional small amount of polyhydroxycompound with phosgen, carbonic acid, or a carbonate diester. Exemplaryaromatic dihydroxy compounds include 2,2-bis(4-hydroxy-phenyl)propane(bisphenol A), tetramethylbisphenol A, tetrabromobisphenol A,bis(4-hydroxyphenyl)-p-diisopropyl-benzene, hydroquinone, resorcinol,4,4'-dihydroxydiphenyl, bis(4-hydroxyphenyl)sulfide,bis(4-hydroxyphenyl)ketone, 1,1-bis(4-hydroxyphenyl)ethane,1,1-bis(4-hydroxyphenyl)-cyclohexane, among which the bisphenol A beingthe preferred in view of the heat resistance, mechanical strength, andmolding properties. Such dihydroxy compound may be used either alone orin combination of two or more. Preferred combinations of two or moredihydroxy compounds include bisphenol A with tetramethylbisphenol A; andbisphenol A with tetrabromobisohenol A.

The polycarbonate resin used in the present invention may preferablyhave a melt index in the range of from 1 to 30, and more preferably,from 4 to 20. Use of a polycarbonate resin with a melt index of lessthan 1 may result in poor molding properties, while an excessively highmelt index may result in a reduced impact strength of the resultingproduct.

The polycarbonate resin used in the present invention may contain acrystalline or non-crystalline thermoplastic resin such as polyethyleneterephthalate, polybutylene terephthalate, bisphenol polyarylate,6,6-Nylon, 6-Nylon, 6,10-Nylon or the like in an amount that would notadversely affect the merits of the present invention, preferably in anamount of up to 20% by weight, and more preferably in an amount of up to10% by weight. incorporation of a crystalline resin will result in animproved chemical resistance, and incorporation of a non-crystallineresin will result in an improved heat resistance.

The resin composition of the present invention may contain suchpolycarbonate resin preferably in an amount of from 40 to 99% by weight,and more preferably from 60 to 95% by weight, and most preferably from80 to 95% by weight. An excessively low content of the polycarbonateresin will result in poor heat resistance and impact strength of theresin composition, whereas an excessively large content of thepolycarbonate resin will result in poor workability upon molding. Themolecular weight of the polycarbonate resin is not limited to anyparticular range. However, the polycarbonate resin may preferably have anumber average molecular weight of from 1,000 to 100,000, and morepreferably, from 5,000 to 40,000 calculated in terms of polystyrene. Themolecular weight lower than such range may adversely affect the impactstrength and other physical properties of the resin composition, whilethe molecular weight larger than such range will result in deterioratedworkability upon molding. However, when the polycarbonate resin is usedfor the purpose of improving the heat resistance, rigidity, and flameretardancy of the polyolefin resin, the content of the polycarbonateresin may be not necessarily exceed 40% by weight.

(B) Polyolefin resin

The polyolefin resins which may be used in the present invention includecrystalline polypropylene, crystalline propylene-ethylene block orrandom copolymer, low density polyethylene, high density polyethylene,linear low density polyethylene, ultra-high molecular weightpolyethylene, ethylene-propylene random copolymer,ethylene-propylene-diene copolymer, and the like. Among such polyolefinresins, the preferred are the crystalline polypropylene, the crystallinepropylene-ethylene copolymer, the low density polyethylene, the highdensity polyethylene, the linear low density polyethylene, and theultra-high molecular weight polyethylene.

The resin composition of the present invention may contain thepolyolefin resin preferably in an amount of from 60 to 0% by weight,more preferably from 60 to 0.1% by weight, still more preferably from 50to 3% by weight, and most preferably from 20 to 3% by weight. Anexcessively large content of the polycarbonate resin will result inreduced heat resistance. The melt index of the polyolefin resin is notlimited to any particular range. However, the polyolefin resin maypreferably have a melt index (at 230° C., under a load of 2.16 kg) offrom 0.1 to 70 g/10 min., and more preferably, from 0.5 to 30 g/10 min.The melt index lower than such range will result in deteriorated moldingWorkability, whereas the melt index higher than such range will resultin poor physical properties, in particular, poor impact strength of theresin composition. However, when the resin composition is provided forthe purpose of improving the heat resistance, rigidity, and flameretardancy of the polyolefin resin, the content of the polyolefin resinmay exceed 60% by weight of the resin composition.

(C) Polyolefin resin modified With at least one functional groupselected from the group consisting of epoxy, carboxyl, and an acidanhydride groups

The modified polyolefin resin used in the present invention is notlimited to any particular species, and it may be any polyolefin resindescribed in the above (B) to which an unsaturated monomer containingepoxy, carboxyl, or an acid anhydride group is copolymerized.

Exemplary epoxy-containing unsaturated monomers include glycidylmethacrylate, butylglycidyl malate, butylglycidyl fumarate,propylglycidyl malate, glycidyl acrylate, N-4-(2,3-epoxypropoxy)-3,5-dimethylbenzyl!-acrylamide, and the like. Amongthese, the preferred are glycidyl methacrylate and N-4-(2,3-epoxypropoxy)-3,5-dimethylbenzyl!acrylamide in view of theirprice and availability.

Exemplary carboxyl-containing unsaturated monomers include acrylic acid,methacrylic acid, maleic acid, and the like. Exemplary unsaturatedmonomers containing an acid anhydride group are maleic anhydride,itaconic anhydride, citraconic anhydride, and the like. Among these,acrylic acid and maleic anhydride are the preferred in view of theirreactivity and availability.

The unsaturated monomer containing epoxy, carboxyl, or an acid anhydridegroup may be copolymerized with the polyolefin resin by any desiredmeans. Exemplary means include melt kneading of the polyolefin resin andthe unsaturated monomer in a twin screw extruder, a Banbury mixer, akneader or the like in the presence or absence of a radical initiator,and copolymerization by the copresence of the monomer constituting thepolyolefin with the unsaturated monomer containing epoxy, carboxyl, oracid anhydride. The content of the unsaturated monomer is in the rangeof from 0.01 to 10% by weight, and preferably, from 0.1 to 5% by weightof the modified polyolefin resin. The content of the unsaturated monomerlower than such range is insufficient to improve the delaminationresistance of the resulting resin composition, and the content in excessof such range will adversely affect such properties as long-term heatresistance.

The content of the polyolefin resin modified with epoxy, carboxyl, or anacid anhydride group is preferably in the range of from 0.5 to 60% byweight, more preferably, from 0.5 to 30% by weight, and most preferably,from 0.5 to 20% by weight of the resin composition of the presentinvention. The content of the modified polyolefin resin lower than suchrange will result in a reduced polycarbonate/polyolefin compatibility ofthe resulting resin composition, leading to susceptibility fordelamination. The content in excess of such range will adversely affectsuch properties as heat resistance. However, when the resin compositionis provided for the purpose of improving the heat resistance, rigidity,and flame retardancy of the polyolefin resin, the content of themodified polyolefin resin may exceed 60% by weight of the resincomposition.

(D) Compound represented by at formula: HOOC--R--NH₂

In the compound represented by the formula: HOOC--R--NH₂ used in thepresent invention, R represents a structural unit selected from analkene group, an alkylidene group, and an oligomethylene groupcontaining 5 or more carbon atoms, and phenylene group and naphthylenegroup. Upper limit in the number of carbon atoms contained in suchcompound is not limited to any particular number. However, such compoundmay preferably contain up to 20 carbon atoms, and more preferably, up to12 carbon atoms. The compound containing an excessively large number ofcarbon atoms is difficult to obtain in an industrial scale, and willresult in poor heat resistance of the resulting compound. The alkylidenegroup may be linear, branched or alicyclic. The phenylene group may bep-phenylene, m-phenylene, or o-phenylene. The naphthylene group may be2,6-naphthylene group, 2,7-naphthylene group, 1,5-naphthylene group,1,8-naphthylene group, or 4,4'-diphenylene group. The phenylene groupand the naphthylene group may be optionally substituted with an alkylgroup, carboxyl group, a halide, amino group, and an alkoxy group.

Exemplary such compounds include 6-aminocaproic acid, 7-aminoheptanoicacid, 8-aminooitanoic acid, 11-aminoundecanoic acid, p-aminobenzoicacid, m-aminobenzoic acid, 2-amino-6-naphthalenecarboxylic acid,2-amino-7-naphthalenecarboxylic acid.

The content of the compound represented by the formula: HOOC--R--NH₂ maybe in the range of from 0.05 to 5% by weight, preferably from 0.05 to 4%by weight, and more preferably, from 0.05 to 2% by weight of the resincomposition of the present invention. An excessively low content of suchcompound will result in an insufficient compatibility of the resincomponents, and hence, in delamination. An excessively large content ofsuch compound will particularly result in the reduced molecular weightof the polycarbonate component, leading to the poor impact strength ofthe resulting composition.

(E) Styrene copolymer

The styrene copolymer used in the present invention may be a copolymerof styrene with an olefin or butadiene, which is either a block, agraft, or an alternating copolymer. Exemplary block copolymers includestyrene-ethylene/propylene copolymer, styrene-butadiene-styrenecopolymer, styrene-ethylene/butylene-styrene copolymer, and the like.Exemplary grafted copolymers include polystyrene-grafted polypropylene,polystyrene/polyacrylo-nitrile-grafted polypropylene,polystyrene-grafted low density polyethylene,polystyrene/polyacrylonitrile-grafted low density polyethylene, and thelike. Exemplary alternating copolymers include styrene-butadienecopolymer and the like.

The content of the styrene copolymer is in the range of from 0.1 to 30%by weight, and preferably, from 0.5 to 10% by weight. When the contentof the styrene copolymer is lower than such range, effect of theaddition would not be significant, and when the content is in excess ofsuch range, heat resistance and flexural rigidity of the resulting resinwould be reduced.

The resin composition of the present invention may include variouscomponents other than the above-described components in an amount wouldnot interfere with the merits of the present invention. Exemplary suchadditional components that may be added include other thermoplastic andnon-thermoplastic resin components, elastomers, pigments, organic andinorganic fillers, and the like. Examples of the thermoplastic resinsare polyethylene terephthalate, polybutylene terephthalate, Nylon,modified PPO, polystyrene, liquid crystal resin, Teflon, and the like.Examples of the resin components that are not thermoplastic are siliconeoil, and the like. Examples of the inorganic fillers are alamid fiber,carbon fiber, talc, mica, calcium carbonate, potassium titanate whisker,and the like. The resin composition of the present invention may furthercomprise a flame retardant, a plasticizer, an antioxidant, or otheradditives that are generally added to a thermoplastic resin. Suchadditives may be used in appropriate amounts.

1-2! The resin composition comprising (A), (C) and (D) according to thefirst embodiment exhibits an improved polycarbonate/polyolefincompatibility, and therefore, the properties inherent to thepolycarbonate can be readily balanced with the properties inherent tothe polyolefin. The product produced therefrom exhibits reduceddelamination.

1-3! The resin composition comprising (A), (B), (C) and (D) according tothe second embodiment has excellent heat resistance, mechanicalstrength, and surface properties (no delamination).

1-4! The resin composition comprising (A), (B), (C), (D) and (E)according to the third embodiment has excellent heat resistance,mechanical strength, and surface properties (improved delaminationresistance) comparable to those of the resin composition according tothe second embodiment, as well as improved impact resistance and moldingproperties.

1-5! The favorable resin composition according to the present inventionthat comprises

component (A) in an amount of preferably from 40 to 99% by weight, morepreferably from 60 to 95% by weight, and most preferably from 80 to 95%by weight;

component (B) in an amount of preferably from 60 to 0% by weight, morepreferably from 50 to 0.1% by weight, still more preferably from 50 to3% by weight, and most preferably from 20 to 3% by weight;

component (C) in an amount of preferably from 0.5 to 60% by weight, morepreferably from 0.5 to 30% by weight, and most preferably from 0.5 to20% by weight; and

component (D) in an amount of preferably from 0.05 to 5% by weight, morepreferably from 0.05 to 4% by weight, and most preferably from 0.05 to2% by weight; has well balanced mechanical strength, heat resistance,wear resistant properties, and solvent resistance.

Such resin composition may further comprise optional component (E) in anamount of preferably from 0.1 to 30% by weight, more preferably from 0.5to 10% by weight, and most preferably from 0.5 to 5% by weight.

The favorable resin composition according to the present invention thatcomprises

component (A) in an amount of preferably from 1 to 99% by weight, morepreferably from 1 to 60% by weight, and most preferably from 3 to 20% byweight;

component (B) in an amount of preferably from 98 to 0% by weight, morepreferably from 90 to 0% by weight, and most preferably from 10 to 0% byweight;

component (C) in an amount of preferably from 0.5 to 99% by weight, morepreferably from 10 to 95% by weight, and most preferably from 20 to 90%by weight; and

component (D) in an amount of preferably from 0.05 to 5% by weight, morepreferably from 0.05 to 4% by weight, and most preferably from 0.05 to2% by weight; has highly improved solvent resistance.

Such resin composition may further comprise optional component (E) in anamount of preferably from 0.1 to 30% by weight, more preferably from 0.5to 10% by weight, and most preferably from 0.5 to 5% by weight.

2! According to the second aspect of the present invention whereby theabove-described second object of the present invention is attained,there is provided processes for producing resin compositions accordingto the first aspect of the present invention.

The components (A) to (E) used in such processes have been described inthe above 1!. The processes for producing resin compositions of thepresent invention are characterized in that the process advances via thereaction stages of production of a precursor of a compatibilizer for thepolycarbonate resin (A) and the polyolefin resin (B) by melt kneading;and production of the compatibilizer for the polycarbonate resin (A) andthe polyolefin resin (B) by melt kneading of the precursor with thepolycarbonate resin (A). The latter reaction stage wherein thecompatibilizer is produced may be carried out either subsequent to orsimultaneously with the former reaction stage wherein the compatibilizerprecursor is produced. It is also possible to simultaneously conduct theproduction of the compatibilizer precursor and the production of thecompatibilizer in the course of the production of the resin compositionof the present invention. The compatibilizer precursor and thecompatibilizer will be described later.

More illustratively, when the modified polyolefin resin (C) used is thepolyolefin resin modified with at least one functional group selectedfrom the group consisting of carboxyl and an acid anhydride groups, theprocess of the present invention advances through the reaction stages of

reaction of the carboxyl- or acid anhydride-modified polyolefin resin(C) with the compound (D) represented by the formula: HOOC--R--NH₂, inwhich the linkage represented by formula (H): ##STR3## having thefunctional moiety (H) is formed; and reaction of such moiety (H) withthe polycarbonate resin (A).

When the modified polyolefin resin (C) used is the polyolefin resinmodified with epoxy group, the process of the present invention advancesthrough the reaction stages of

reaction of the epoxy-modified polyolefin resin (C) with the compound(D) represented by the formula: HOOC--R--NH₂, in which the linkagerepresented by formula (J): ##STR4## having the functional moiety (J) isformed; and reaction of such moiety (J) with the polycarbonate resin(A).

Accordingly, in the production of the resin compositions of the presentinvention,

the precursor of the compatibilizer for the polycarbonate resin (A) andthe polyolefin resin (B); and

the compatibilizer formed from such compatibilizer precursor

are formed as intermediates, whose definitions are given below.Production of the resin composition of the present invention throughformation of functional moiety (H) Is preferred in view of the minimizedunfavorable side reaction.

Precursor of the Compatibilizer for the Polycarbonate Resin (A) and thePolyolefin Resin (B)

The compatibilizer precursor is produced through the reaction of

(C) a polyolefin resin that has been modified with at least onefunctional group selected from the group consisting of epoxy, carboxyl,and an acid anhydride groups; and

(D) a compound represented by the formula: HOOC--R--NH2 wherein Rrepresents at least one member selected from the group consisting of analkene group, an alkylidene group, and an oligomethylene groupcontaining 5 or more carbon atoms, and phenylene group and naphthylenegroup optionally substituted with an alkyl group.

Compatibilizer for the Polycarbonate Resin (A) and the Polyolefin Resin(B)

The compatibilizer is produced through the reaction of

(A) a polycarbonate resin;

(C) a polyolefin resin that has been modified with at least onefunctional group selected from the group consisting of epoxy, carboxyl,and an acid anhydride groups; and

(D) a compound represented by the formula: HOOC--R--NH₂ wherein Rrepresents at least one member selected from the group consisting of analkene group, an alkylidene group, and an oligomethylene groupcontaining 5 or more carbon atoms, and phenylene group and naphthylenegroup optionally substituted with an alkyl group.

Since such intermediates are formed in the melt kneading of the startingmaterials, the resin composition of the present invention would undergoa sufficient polymer alloying to exhibit improved compatibility, as ifthe polycarbonate resin and the polyolefin resin had undergone graftpolymerization. Such reaction can be promoted simultaneously with themixing of various starting materials in a twin screw extruder through socalled reactive processing. Production efficiency of a quite high levelis thereby attained.

The reason for the compatibility of the compatibilizer produced in thepresent invention to serve an efficient compatibilizer for thepolycarbonate and the polyolefin is estimated as follows.

The --NH₂ group in the component (D) reacts with the carboxyl group orthe acid anhydride group in the component (C) to form amide bond, oralternatively, with the epoxy group in the component (C) to form aminobond, and the component (D) would then become added to the component (C)and the carboxyl group in the component (D) would become incorporatedinto the component (C) with the intervening amide or amino bond. Thecarboxyl group in the component (D) that has been incorporated into thecomponent (C) then reacts with the carboxyl group in the component (A),and then, a polycarbonate-grafted polyolefin wherein the polycarbonate(A) and the component (C) are linked by ester bond; polycarbonate havingterminal hydroxyl group; and CO₂ are formed by decomposition. The thusformed polycarbonate-grafted polyolefin has the polycarbonate moiety andthe polyolefin moiety within its molecule, and therefore, thepolycarbonate-grafted polyolefin may serve an effective compatibilizerfor the polycarbonate/polyolefin-based resin composition.

The compatibilizer of the highest effectivity may be obtained byreacting a stoichiometric amount of the component (C) in terms of itsfunctional groups, the component (D) and the component (A), and by usingthe component (A) and the polyolefin in the component (C) of higherpolymerization degrees.

In the production of the resin compositions of the present invention,melt kneading of the starting materials to promote the polymer alloyingmay be carried out with a single screw extruder, a twin screw extruder,kneader, Brabender, or the like. Use of a twin screw extruder ispreferable for the efficiency of the alloying. The reaction, namely, themelt kneading may preferably be carried out at a temperature in therange of from 265° to 380° C., and more preferably, from 270° to 340° C.

The melt kneading temperature of lower than 265° C. is insufficient topromote sufficient compatibilization between the polycarbonate resin andthe polyolefin resin, and the resulting resin composition would besusceptible for delamination upon molding. The melt kneading temperatureof higher than 380° C. would result in thermal decomposition of theresin composition, and the resulting product would exhibit poormechanical properties.

If desired, some of the starting materials may be preliminarily meltkneaded before the addition to the melt kneader of the remainingstarting materials. For example, a portion of the polycarbonate resin(A) and the compound (D) represented by the formula: HOOC--R--NH₂ may bepreliminarily melt kneaded before the addition of the remaining startingmaterials. In such case, the compatibilizer precursor would be formedduring the preliminary melt kneading, and in the subsequent meltkneading, such compatibilizer precursor converted into thecompatibilizer would be blended with the polycarbonate resin (A) and theoptional styrene copolymer (E) to form the matrix of the resulting resincomposition, in which the polyolefin resin is dispersed in microparticulate composite. The polyolefin particles may preferably have amicroscopically determined average particle size in one range of from0.1 μm to 5 μm, and an average aspect ratio (major axis/minor axis) ofup to 5.

Next, the reaction stages characteristic to the present invention aredescribed.

(1) The step wherein the polyolefin resin (C) that has been modifiedwith at least one functional group selected from the group consisting ofepoxy, carboxyl, and an acid anhydride groups is modified by thecompound (D) represented by the formula: HOOC--R--NH₂ to produce theprecursor for the polycarbonate/polyolefin compatibilizer.

In this step, 100% by weight of the polyolefin resin (C) that has beenmodified with at least one functional group selected from the groupconsisting of epoxy, carboxyl, and an acid anhydride groups is uniformlymixed with the compound (D) represented by the formula: HOOC--R--NH₂preferably used in an amount of from 0.05 to 5% by weight in Henschelmixer, and the mixture is fed to a melt kneader such as a twin screwextruder or a kneader machine wherein the mixture is melt kneaded at atemperature preferably in the range of from 180° to 340° C.

When the amount of the compound (D) represented by the formula:HOOC--R--NH₂ is less than 0.05% by weight, the improvement in thepolycarbonate/polyolefin compatibility would be insufficient. Amount ofthe compound (D) excess of 5% by weight would adversely affect the heatresistance of the resulting product. The reaction temperature (kneadingtemperature) below the above-specified range would result in anexcessively low reaction rate, and hence, in an insufficient reaction,while the reaction temperature in excess of such range would result insignificant deterioration of the resin composition to result insignificantly poor physical properties or the resulting product.

(2) The step wherein the polycarbonate/polyolefin compatibilizerprecursor produced in step (1) is melt kneaded with the polycarbonateresin, and optionally, with the polyolefin resin.

In this step, the HOOC--R--NH₂ --modified polyolefin resin produced instep (1) preferably in an amount of from 2 to 40% by weight; thepolyolefin resin preferably in an amount of from 0 to 20% by weight; andthe polycarbonate resin preferably in an amount of from 60 to 99% byweight are preliminarily mixed in Henschel mixer to form a uniformmixture, and the resulting mixture is fed to a twin screw extruder, akneader machine, or the like wherein the mixture is melt kneaded at atemperature preferably in tee range of from 220° to 340° C.

When the amount of the compatibilizer precursor blended is less than theabove-specified range, the compatibility would not be sufficientlyimproved. On the other hand, an excessively large amount of thecompatibilizer precursor would adversely affect the heat resistance ofthe resulting product. The amount used of the polycarbonate resin lessthan the above-specified range would result in poor heat resistance ofthe resulting product, while excessive use of the polycarbonate resinwould result in poor organic solvent resistance. The kneadingtemperature below the above-specified range would result in aninsufficient melting of the resin components to interfere with theuniform dispersion of the components, while the kneading temperature inexcess or such range would result in significant deterioration of theresin composition to result in significantly poor physical properties ofthe resulting product.

The processes for producing the resin compositions of the presentinvention according to the second aspect of the present inventioninclude the following seven embodiments.

2-1! In the production process according to the first embodiment, theresin composition is produced by melt kneading the predetermined amountsof the components (A) to (D) and the optional component (E).

The resin production by such procedure is simple, and therefore,favorable in view of the low production cost.

2--2! In the production process according to the second embodiment, theresin composition is produced by melt kneading the compatibilizerprecursor as describe above with the polycarbonate resin (A).

The resin production by such procedure has the merit of a suppresseddecomposition of the polycarbonate resin, and the resulting productwould have an improved impact strength.

2-3! In the production process according to the third embodiment, theresin composition is produced by melt kneading the compatibilizerprecursor as described above with the polycarbonate resin (A.), thepolyolefin resin (B) and the styrene copolymer resin (E) simultaneouslyor sequentially in an arbitrary order.

Production of the resin composition by such procedure is convenient forregulating the polycarbonate/polyolefin compatibility, and hence, forregulating the properties of the resulting product.

2-4! In the production process according to the fourth embodiment, theresin composition is produced by melt kneading the compatibilizer asdescribed above with the polycarbonate resin (A).

Production of the resin composition by such procedure is also convenientfor regulating the polycarbonate/-polyolefin compatibility, and hence,for regulating the properties of the resulting product.

2-5! In the production process according to the fifth embodiment, theresin composition is produced by melt kneading the compatibilizer asdescribed above with the polycarbonate resin (A), the polyolefin resin(B) and the styrene copolymer resin (E) simultaneously or sequentiallyin an arbitrary order.

Production of the resin composition by such procedure is also convenientfor regulating the polycarbonate/polyolefin compatibility, and hence,for regulating the properties of the resulting product.

2-6! In the production process according to the sixth embodiment, theresin composition is produced by melt kneading the polyolefin resin (B),an acid anhydride, and the compound (D) represented by the formula:HOOC--R--NH₂ wherein R represents at least one member selected from thegroup consisting of an alkene group, an alkylidene group, and anoligomethylene group containing 5 or more carbon atoms, and phenylenegroup and naphthylene group optionally substituted with an alkyl group;and continuing the melt kneading after adding the polycarbonate resin(A) and the styrene copolymer resin (E) simultaneously or sequentiallyin an arbitrary order.

The resin production by such procedure has the merit of a suppresseddecomposition of the polycarbonate resin, and the resulting productwould have an improved impact strength.

2-7! In the production process according to the seventh embodiment, theresin composition is produced by melt kneading the polycarbonate resin(A) and the compound (D) represented by the formula: HOOC--R--NH₂wherein R represents at least one member selected from the groupconsisting of an alkene group, an alkylidene group, and anoligomethylene group containing 5 or more carbon atoms, and phenylenegroup and naphthylene group optionally substituted with an alkyl group;and continuing the melt kneading after adding at least one componentselected from the group consisting of the polycarbonate resin (A), thepolyolefin resin (B), and the polyolefin resin (C) that has beenmodified with at least one functional group selected from the groupconsisting of epoxy, carboxyl, and an acid anhydride groups in anarbitrary order.

The resin production by such procedure has the merit of an improvedpolycarbonate/polyolefin compatibility, and the resulting product wouldexhibit an improved resistance to delamination.

The resin compositions of the present invention may be molded intodesired products by any of the conventional procedures used in moldingthermoplastic resins, for example, injection molding, blow molding,sheet forming, laminate molding, and stamping, among which the injectionmolding being preferred.

When the process for producing the resin composition of the presentinvention is employed, a polycarbonate/polyolefin based resincomposition with excellent heat resistance, mechanical strength, andappearance (with no delamination) may be produced from readily availablestarting materials at a high production efficiency. Such excellentphysical and surface properties may be attributed to the improvedpolycarbonate/polyolefin compatibility through chemical reaction betweenthe components (C) and (D). The improved polycarbonate/polyolefincompatibility through chemical reaction between the components (C) and(D) is manifested by the microphotographs of the cross section, as willbe described later.

3! According to the third aspect of the present invention whereby theabove-described third object of the present invention is attained, thereis provided molded materials wish improved wear resistant properties.

Such molded materials are produced by melt molding the resincompositions according to the first aspect of the present inventiondescribed in the above 1!. The molded materials with improved wearresistant properties according to this aspect of the invention also hasexcellent heat resistance, mechanical properties, and flame retardancy,and may be produced in an inexpensive manner.

The resin composition employed for the production is not particularlylimited. Preferable resin composition employed comprises

99 to 85% by weight, and preferably, 98 to 90% by weight of thepolycarbonate (A);

1 to 15% by weight, and preferably, 2 to 10% by weight of the modifiedpolyolefin (C); and

0.05 to 2% by weight, and preferably, 0.1 to 2% by weight of thecompound (D) represented by the formula: HOOC--R--NH₂.

The resin composition may further comprise the polyolefin (B) preferablyin an amount of from 1 to 5% by weight in addition to the component (A),(C) and (D). The component (B) contributes for the improvement in themolding properties of the resin composition.

If desired, the resin composition may further comprise the styrenecopolymer resin (E) preferably in an amount of from 1 to 5% by weight.The component (E) contributes for the improvement in the impact strengthof the molded material.

The polycarbonate/polyolefin based resin composition employed forproducing the molded material with improved wear resistant propertiesmay be produced by blending the polycarbonate (A), the modifiedpolyolefin (C); and the compound (D) represented by the formula:HOOC--R--NH₂ in the blending ratio of:

99 to 85% by weight of (A);

1 to 15% by weight of (C); and

0.05 to 2% by weight (D);

Preferable blending ratio is:

98 to 90% by weight of (A);

2 to 10% by weight of (C); and

0.1 to 1% by weight of (D).

The most preferable blending ratio is

93 to 97% by weight of (A);

3 to 7% by weight of (C); and

0.2 to 1.0% by weight of (D).

When the content of the polycarbonate resin (A) exceeds 99% by weight,the content of the modified polyolefin (C) would be reduced to result inpoor wear resistant properties. When the content of the modifiedpolyolefin (C) exceeds 15% by weight, the resulting resin compositionwould exhibit somewhat reduced polycarbonate/polyolefin compatibility aswell as poor heat resistance. The content of the compound (D) of lessthan 0.05% by weight would result in insufficient wear resistantproperties, while the content in excess of 2 by weight would induce areaction between the compound (D) and the polycarbonate to particularlyresult in the reduced molecular weight of the polycarbonate. Suchreduction in the molecular weight of the polycarbonate component wouldinvite reduced impact strength of the resulting product.

The modified polyolefin (C) may preferably be a modified polyethylene.

The modified polyethylene used in this aspect of the invention is notlimited to any particular species so long as the modified polyethyleneis high density polyethylene, low density polyethylene, straight-chainlow density polyethylene, or the like having copolymerized therewith anunsaturated monomer containing an acid, an acid anhydride, or epoxygroup. Exemplary unsaturated monomers containing an acid include acrylicacid, methacrylic acid, maleic acid, cyclohexenedicarboxylic acid, andthe like. Exemplary acid anhydride groups include maleic anhydride,itaconic anhydride, citraconic anhydride, cyclohexenedicarboxylicanhydride, and the like. Exemplary preferable epoxy-containingunsaturated monomers include glycidyl methacrylate, butylglycidylmalate, butylglycidyl fumarate, propylglycidyl malate, glycidylacrylate, N- 4-(2,3-epoxypropoxy)-3,5-dimethylbenzyl!acrylamide, and thelike.

The unsaturated monomer containing an acid, an acid anhydride, or epoxygroup may be copolymerized with the high density polyethylene, the lowdensity polyethylene, the straight-chain low density polyethylene, orthe like by any desired means. Exemplary means include melt kneading ofthe polyethylene resin with the unsaturated monomer in a twin screwextruder, a Banbury mixer, a kneading machine, or the like in thepresence or absence of a radical initiator, and copolymerization by thecopresence of the monomer constituting the polyethylene with theunsaturated monomer containing epoxy, carboxyl, or acid anhydride.

Preferably, the acid, the acid anhydride, or the epoxy group may bepresent at a content in the range of from 0.01 to 10% by weight of thepolyethylene resin. A content lower than such range would result ininsufficient wear resistant properties of the resulting product, and acontent in excess of such range would induce such problems as coloringof the material. The content of the polyethylene resin modified with anacid, an acid anhydride or epoxy group is in the range of from 1 to 15%by weight, preferably from 2 to 10% by weight, and more preferably, from3 to 7% by weight of the resin composition of the present invention. Acontent of the modified polyethylene resin lower than such range willresult in insufficient wear resistant properties, whereas a content inexcess of such range will result in a reduced resistance todelamination.

The polyethylene used in producing the modified polyethylene maypreferably be straight-chain low density polyethylene, low densitypolyethylene, or high density polyethylene; and more preferably,straight-chain low density polyethylene or low density polyethylene; andmost preferably, straight-chain low density polyethylene. Use of thepreferred polyethylene is effective in improving the wear resistantproperties of the resulting product.

The modified polyethylene employed is not limited in terms of itsmolecular weight. However, the modified polyethylene may preferably havea melt index, MI in the range of from 0.1 to 20, and more preferably,from 0.2 to 10. Use of the modified polyethylene with a melt index lowerthan such range would result in poor molding properties, and use of themodified polyethylene with a melt index in excess of such range wouldresult in insufficient wear resistant properties of the resultingproduct.

The molded material having improved wear resistant properties accordingto the third aspect of the present invention may be prepared by blendingthe structural units as described above in the predetermined amount;melt kneading the mixture to produce the resin composition; and meltmolding the resin composition. The thus molded material has excellentwear resistant properties, mechanical strength, and heat resistance in agood balance. The mechanism through which such favorable balancedproperties are invited is not definitely found out. However, it isestimated that reaction of the compound (D) represented by the formula:HOOC--R--NH₂ with the polycarbonate resin (A) and the modifiedpolyolefin resin (C) has invited the improved compatibility between thepolycarbonate resin (A) and the modified polyolefin resin (C), leadingto the improved wear resistant properties and the mechanical strength.

In an exemplary production process, the starting materials may beuniformly mixed in a blender such as Henschel mixer, ribbon blender, ortwin-cylinder blender, and the resulting mixture may be melt kneaded ina single or twin screw extruder, a kneader machine, Banbury mixer,Brabender Plasti-Corder, or the like. It is also possible topreliminarily melt knead two of the starting materials, and add theremaining material afterwards. Particularly preferred is the processwherein the modified polyolefin resin (C) and the compound (D)represented by the formula: HOOC--R--NH₂ are preliminarily melt kneaded,and the polycarbonate resin (A) is added afterwards. Impact strength ofthe molded article would be improved by adopting such a process. Theimproved impact strength is probably attained by inhibition in themolecular weight reduction of the polycarbonate resin (A) caused by thereaction between the modified polyolefin resin (C) and the compound (D)represented by the formula: HOOC--R--NH₂.

The molded material according to this aspect of the invention may beprepared by melt molding the above-described resin composition by any ofthe conventional procedures used in molding thermoplastic resins, forexample, injection molding, blow molding, sheet forming, laminatemolding, and press molding, among which the injection molding beingpreferred. The injection molding may be carried out at a melttemperature of from 240° to 360° C. and a mold temperature of from 40°to 130° C.

In the molded material according to this aspect of the presentinvention, the polyethylene is preferably dispersed in particulate formin the polycarbonate, and the particulate polyethylene present in theregion from the material surface to a depth of 20 μm may preferably havean average aspect ratio (major axis/minor axis) of up to 5. When theaspect ratio of the particulate polyolefin is in excess of 5, theresulting product will have insufficient wear resistant properties,probably due to the increased abrasion caused by its laminar, peelablesurface structure. The preferable dispersion of the polyethylene in thepolycarbonate as described above may be attained when the amount blendedof the polycarbonate resin is 90% by weight or more, the modifiedpolyethylene is up to 10% by weight, and the compound (D) represented bythe formula: HOOC--R--NH₂ is 0.05 to 2.0% by weight. However, themicrophase structure may become altered by such factors as moldingtemperature, injection speed, and cooling rate.

The molded materials according to this aspect of the present inventionmay further include inorganic fillers such as glass fiber, carbon fiber,alamid fiber, talc, mica, calcium carbonate, and the like at a contentthat would not adversely affect the merits of the invention. Inclusionof glass fiber, carbon fiber, alamid fiber, or the like is particularlypreferred for improving flexural rigidity and wear resistant propertiesof the resulting product. Inclusion of additives such as silicone oil,ultra-high molecular weight polyethylene powder, unmodifiedpolyethylene, homopolypropylene, polyethylene-polypropylene copolymer,molybdenum compounds, or the like is also preferable for improving thewear resistant properties of the resulting product. The molded materialmay also contain additives such as a flame retardant, a plasticizer, anantioxidant, and the like that are generally added to a thermoplasticresin, which are used in appropriate amounts.

The molded material according to this aspect of the present inventionwith improved wear resistant properties may be used for the parts ofoffice automation equipment, household appliance, and medical equipment,and the like. Use for such parts as gear, cum, and bearing isparticularly preferred.

4! According to the fourth aspect of the present invention whereby theabove-described fourth object of the present invention is attained,there is provided molded materials with improved solvent resistance.

Such molded materials with improved solvent resistance are produced bymelt molding the resin compositions according to the first aspect of thepresent invention described in the above 1!. The molded materials withimproved solvent resistance according to this aspect of the inventionalso has excellent heat resistance, mechanical properties, and flameretardancy, and may be produced in an inexpensive manner.

The resin composition employed for the production is not particularlylimited. The resulting product will have well balanced mechanicalstrength, heat resistance and solvent resistance when the resincomposition comprises

99 to 85% by weight, and preferably, 98 to 90% by weight of thepolycarbonate (A);

1 to 15% by weight, and preferably, 2 to 10% by weight of the modifiedpolyolefin (C); and

0.05 to 2% by weight, and preferably, 0.1 to 2% by weight of thecompound (D) represented by the formula: HOOC--R--NH₂.

The resin composition may further comprise the polyolefin (B) preferablyin an amount of from 1 to 5% by weight in addition to the component (A),(C) and (D). The component (B) contributes for the improvement in themolding properties of the resin composition. If desired, the resincomposition may further comprise the styrene copolymer resin (E)preferably in an amount of from 1 to 5% by weight. The component (E)contributes for the improvement in the impact strength.

The modified polyolefin (C) used in this aspect of the invention maypreferably be polypropylene modified with maleic anhydride,straight-chain low density polyethylene modified with maleic anhydride,low density polyethylene modified with maleic anhydride, or high densitypolyethylene modified with maleic anhydride in view of theiravailability at a relatively low price.

The molded material according to this aspect of the present inventionmay further include inorganic fillers such as glass fiber, carbon fiber,alamid fiber, talc, mica, calcium carbonate, and the like at a contentthat would not adversely affect the merits of the invention. The moldedmaterial may also include an unmodified polyolefin such ashomopolypropylene, polyethylene-polypropylene block copolymer,polyethylene-polypropylene random copolymer, high density polyethylene,low density polyethylene, straight-chain low density polyethylene,ultra-high molecular weight polyethylene powder, polymethylpentene, orthe like. The molded material may also contain additives such as a flameretardant, a plasticizer, an antioxidant, and the like that aregenerally added to a thermoplastic resin, which are used in appropriateamounts.

In the molded material with improved solvent resistance according tothis aspect of the present invention, the polyolefin is preferablydispersed in the polycarbonate matrix phase in microparticulate phase,and the particulate polyolefin present in the region from the materialsurface to a depth of 20 μm may preferably have an average particle sizein the range of from 0.1 to 3 μm and an average aspect ratio (majoraxis/minor axis) of up to 5. Such microphase structure results in themechanical strength and the heat resistance of the material in goodbalance with the solvent resistance.

The process for producing the resin composition used is not limited toany particular procedure, and use of the procedure described in theabove 2-6! is preferred in view of the impact strength of the material.

The process employed for the melt molding is not particularly limited,and injection molding at a melt temperature of from 240° to 360° C. anda mold temperature of from 40° to 130° C. is preferred.

The molded material with improved solvent resistance according to thisaspect of the present invention may be used for the parts of officeautomation equipment, household appliance, and medical equipment, andthe like. Use for such parts as gear, cum, and bearing is particularlypreferred.

5! According to the fifth aspect of the present invention whereby theabove-described fifth object of the present invention is attained, thereis provided a glass fiber-reinforced resin composition comprising thepolycarbonate/polyolefin resin composition of the present inventiondescribed in the above 1! further comprising a glass fiber (F), and anarticle molded therefrom.

(F) Glass fiber

The glass fiber used in the present invention is not limited to anyparticular type. Preferred is use of chopped strand having a fiberlength of from about 1 to 10 mm preferably made of an inorganic alkalineglass. Both surface treated and surface untreated glass fibers may beused in the present invention, and use of the glass fiber having itssurface treated with a silane compound is preferred. Exemplary silanecompound used for the surface treatment include vinyl ethoxvsilane,vinyl trichlorosilane, vinyl tris-(β-methoxyethoxysilane),γ-glycidoxypropyltrimethoxysilane, γ-aminopropyltriethoxysilane,γ-methacryloxypropyltrimethoxysilane, andN-β-(aminoethyl)-γ-aminopropyltriethoxysilane, among which the aminosilane compounds being preferred. In general, the surface treatment maybe carried out by bringing the glass fiber into contact with the silanecompound, and such contact treatment may preferably be carried out byusing a mixed solvent of a lower alcohol and water.

The content of the glass fiber in the glass fiber-reinforced resincomposition of the present invention is in the range of from 5 to 40% byweight, and preferably from 10 to 35% by weight in relation to thecontent of the polycarbonate/polyolefin-based resin composition in therange of from 95 to 60% by weight. When the content of the glass fiberis less than 5% by weight, the resulting product would have aninsufficient flexural rigidity. When the content is in excess of 40% byweight, the resulting product would have a reduced impact strength tobecome quite brittle.

The glass fiber-reinforced resin composition according to the fifthaspect of the present invention may be produced by blending thepredetermined amounts of the polycarbonate/polyolefin-based resincomposition as described above and the glass fiber, and the meltkneading the mixture. For example, the polycarbonate resin (A), themodified polyolefin resin (C), the compound (D) represented by theformula: HOOC--R--NH₂, and the glass fiber (F) may be uniformly mixed ina blender such as Henschel mixer, ribbon blender, or twin-cylinderblender, and the resulting mixture may be melt kneaded in a single ortwin screw extruder, a kneader machine, Banbury mixer, BrabenderPlasti-Corder, or the like. It is also possible to preliminarily meltknead few of the starting materials, and add the remaining materialsafterwards. Particularly preferred is the process wherein the modifiedpolyolefin resin (C) and the compound (D) represented by the formula:HOOC--R--NH₂ are preliminarily melt kneaded, and the polycarbonate resin(A) and the glass fiber (F) are added afterwards. Impact strength of theglass fiber-reinforced resin composition would be improved by adoptingsuch a process. The improved impact strength is probably attained byinhibition in the molecular weight loss of the polycarbonate resin (A)caused by the reaction between the modified polyolefin resin (C) and thecompound (D) represented by the formula: HOOC--R--NH₂.

The glass fiber-reinforced resin composition as described above may bemelt molded into a molded article by any of the conventional proceduresused in molding thermoplastic resins, for example, injection molding,blow molding, sheet forming, laminate molding, and press molding, amongwhich the injection molding being preferred.

The thus molded article has excellent wear resistant properties,mechanical strength, and heat resistance in a good balance. Themechanism through which such favorable balanced properties are attainedis not definitely found out. However, it is estimated that reaction ofthe compound (D) represented by the formula: HOOC--R--NH₂ with thepolycarbonate resin (A) and the modified polyolefin resin (C) hasinvited the improved compatibility between the polycarbonate resin (A)and the modified polyolefin resin (C), leading to the improved wearresistant properties and the mechanical strength.

The glass fiber-reinforced resin composition or the article moldedtherefrom according to the fifth aspect of the present invention mayfurther include fillers such as carbon fiber, alamid fiber, talc, mica,calcium carbonate, and the like at a content that would not adverselyaffect the merits of the invention. Inclusion of carbon fiber, alamidfiber, or the like is particularly preferred in order to improveflexural rigidity and wear resistant properties of the resultingproduct. Inclusion of additives such as silicone oil, ultra-highmolecular weight polyethylene powder, unmodified polyethylene,homopolypropylene, polyethylene-polypropylene copolymer, molybdenumcompounds, or the like is also preferable for improving the wearresistant properties of the resulting product. The resin composition orthe article molded therefrom may also contain additives such as a flameretardant, a plasticizer, an antioxidant, and the like that aregenerally added to a thermoplastic resin, which are used in appropriateamounts.

EXAMPLE

The invention is more particularly described by way of examples, whichshould not be construed as limiting the invention thereto. The startingmaterials, devices and assessing methods used in the examples are setout below.

Starting Materials

(A) Polycarbonate (PC)

Caribre 200-20 (melt index MI!=20) made by Sumitomo Dow)

Caribre 200-4 (melt index MI!=4) made by Sumitomo Dow)

(B) Polypropylene (PP)

Noblen W101 (MI=8, homopolymer) made by Sumitomo Chemical Co., Ltd.)

(C) Polyethylene (PE)

Linirex AM0710 (MI=0.3, linear low density polyethylene) made by NipponPetrochemicals Co., Ltd.)

(D) Modified polyolefins

Maleic anhydride-modified polypropylene AP590P made by Mitsubishi KaseiCorporation

Epoxy-modified polypropylene, modified C-900X made by Tonen Corporation

Maleic anhydride-modified polyethylene Admer NF300 made by MitsuiPetrochemical Industries, Ltd.

(E) HOOC--R--NH₂

11-aminoundecanoic acid (Aldrich)

(F) Styrene/ethylene/propylene copolymer, Kraton 1701X made by Shell OilCo.

(G) Ethylene/propylene copolymer, Noblen AH561 made by Sumitomo ChemicalCo., Ltd.

Melt kneading

Twin-screw extruder (TEX30HSST) made by The Japan Steel Works, Ltd.,with a barrel temperature of 300° C. and an output rate of 10 kg/hour.

Injection molding

Injection molding machine, SAV-60-52, made by Sanjo Seiki Co., Ltd.,with a molding temperature of 260° C.

Measurement of physical properties

(1) Flexural modulus of elasticity measured at 23° C. by use ofAutograph of Shimadzu Corp., according to the method described in ASTMD-740.

(2) Notched impact strength measured according to the method describedin ASTM D-256.

(3) Delamination of molded articles evaluated by peel test by bonding acellophane self-adhesive tape (Cellotape- CT-12S of Nichiban Co., Ltd.)on the surface of a molding sample and pulling it off wherein when if aresin piece was clearly observed on the pulled-off cellophaneself-adhesive tape, this sample was evaluated as "x", if a trace resinpiece was observed, the sample was evaluated as "Δ" and if no piece wasobserved, the sample was evaluated as "∘."

(4) Heat distortion temperature measured according to the methoddescribed in ASTM D-648.

(5) Tensile strength measured according to the method described in ASTMD-638.

(6) Bending strength measured according to the method described in ASTMD-790.

(7) Observation of morphology

The strand obtained after extrusion molding was frozen by means ofliquid nitrogen and broken into several pieces, and the section of thethus broken strand was observed through a scanning-type electronmicroscope.

1! Firstly, the invention is described by way of examples with respectto a polycarbonate/polyolefin based resin composition exhibiting goodmiscibility and surface properties according to the first aspect of theinvention.

Example 1

800 g of PC (Caribre 200-4 of Sumitomo Dow), 200 g of epoxy-modifiedpolypropylene and 48.20 g of 11-aminoundecanoic acid (0.1 mole% based onthe polycarbonate) were pre-mixed and supplied to a twin-screw extruder(L/D=42). The barrel temperature of the extruder was set at 300° C. Theresultant resin composition was subjected to injection molding (at acylinder temperature of 260° C. and a mold temperature of 90° C.) andthe resultant molding was tested. The results are shown in Table 1.

Example 2

The general procedure of Example 1 was repeated except that 200 g ofmaleic anhydride-modified polypropylene was used instead of 200 g of theepoxy-modified polypropylene. The results are shown in Table 1.

Example 3

The general procedure of Example 1 was repeated except that 100 g of theepoxy-modified polypropylene and 100 g of ethylene/propylene copolymerwere used instead of 200 g of the epoxy-modified polypropylene. Theresults are shown in Table 1.

Comparative Example 1

The general procedure of Example 1 was repeated except that 200 g ofethylene/propylene copolymer was used instead of 200 g of theepoxy-modified polypropylene. The results are shown in Table 1.

Comparative Example 2

The general procedure of Example 1 was repeated without use of any 11-aminoundecanoic acid. The results are shown in Table 1.

Comparative Example 3

The general procedure of Example 1 was repeated except that the barreltemperature was set at 260° C. The results are shown in Table 1.

                  TABLE 1                                                         ______________________________________                                                             Tensile  Flexural                                                                             Flexural                                 Peel        HDT      Strength Strength                                                                             Modulus                                  Test        (°C.)                                                                           (kgf/mm.sup.2)                                                                         (kgf/mm.sup.2)                                                                       (kgf/mm.sup.2)                           ______________________________________                                        Ex.                                                                           1      ◯                                                                          117.1    5.175  7.804  208                                    2      ◯                                                                          116.7    5.228  8.113  215                                    3      ◯                                                                          115.1    5.170  7.866  213                                    Com. Ex.                                                                      1      X        122.2    4.566  6.739  174                                    2      X        124.5    4.794  7.212  204                                    3      X        124.3    4.738  7.176  197                                    ______________________________________                                    

Example 4

72.4 g of 11-aminoundecanoic acid was added to 3.2 kg of PC (Caribre200-4 of Sumitomo Dow), which had been dried at 120° C. for 8 hours, and0.8 kg of maleic anhydride-modified polypropylene, followed bysufficient mixing by means of a Henschel mixer. The resulting mixturewas molten and kneaded by means of a twin-screw extruder at 300° C. Inthe barrel and the resultant pellets were subjected to injection molding(at a cylinder temperature of 260° C. and a mold temperature of 90° C.).Thereafter, the tests for the physical properties were conductedaccording to the testing methods set out hereinbefore. The results areshown in Table 2.

Example 5

The general procedure of Example 4 was repeated except thatepoxy-modified polypropylene was used instead of the maleicanhydride-modified polypropylene. The results are shown in Table 2.

Comparative Example 4

The general procedure of Example 4 was repeated without use of any11-aminoundecanoic acid thereby obtaining pellets, followed by injectionmolding and testing of physical properties. The results are shown inTable 2.

Example 6

50.3 g of 11-aminoundecanoic acid was added to 5.0 kg of PC (Caribre200-4 of Sumitomo Dow) which had been dried at 120° C. for 8 hours,followed by melt kneading by use of a twin-screw extruder underconditions of 300° C. 0.5 kg of the resultant kneaded mixture was driedat 120° C. for 8 hours, followed by sufficient mixing with 3.5 kg of PC(Caribre 200-20 of Sumitomo Dow) 0.5 kg of polypropylene and 0.5 kg ofepoxy-modified polypropylene by means of a Henschel mixer and meltkneading by use of a twin-screw extruder 260° C. The resultantcomposition was subjected to the tests for the physical properties. Theresults are shown in Table 2.

Comparative Example 5

The general procedure of Example 6 was repeated without use of any11-aminoundecanoic acid, thereby obtaining a composition, followed byconducting the tests for the physical properties. The results are shownin Table 2.

Comparative Example 6

In the same manner as in Example 6 using stearic acid instead of the11-aminoundecanoic acid, there was obtained a composition, followed byconducting the tests for the physical properties.

Comparative Example 7

In the same manner as in Example 6 using homopolypropylene instead ofthe epoxy-modified polypropylene, there was obtained a composition. Theresults of the tests for the physical properties are shown in Table 2.

Example 7

The general procedure of Example 4 was repeated using 2.5 kg of PC(Caribre 200-4 of Sumitomo Dow) and 2.5 kg of maleic anhydride-modifiedpolypropylene, thereby obtaining a composition. The results of the testsfor the physical properties are shown in Table 2.

Comparative Example 8

In the same manner as in Example 7 without use of any 11-aminoundecanoicacid, there was obtained a composition. The results of the tests for thephysical properties are shown in Table 2.

Example 8

72.4 g of 11-aminoundecanoic acid was added to 3.6 kg of PC (Caribre200-4 of Sumitomo Dow), which had been dried at 120° C. for 8 hours, and0.4 kg of maleic anhydride-modified polyethylene, followed by sufficientmixing by means of a Henschel mixer. The resulting mixture was moltenand kneaded by means of a twin-screw extruder under conditions of 300°C. and the resultant pellets were subjected to injection molding (at acylinder temperature of 260° C. and a mold temperature of 90° C.).Thereafter, the tests for the physical properties were conducted. Theresults of the measurements are shown in Table 2.

Comparative Example 9

In the same manner as in Example 8 without use of any 11-aminoundecanoicacid, there was obtained a composition. The results of the measurementsfor the physical properties are shown in Table 2.

Example 9

72.4 g of 11-aminoundecanoic acid was added to 3.1 kg of PC (Caribre200-4 of Sumitomo Dow), which had been dried at 120° C. for 8 hours, 0.7kg of maleic anhydride-modified polypropylene and 0.2 kg ofstyrene/ethylene/propylene copolymer, followed by sufficient mixing bymeans of a Henschel mixer. The resulting mixture was melt kneaded bymeans of a twin-screw extruder under conditions of 300° C. and theresultant pellets were subjected to injection molding (at a cylindertemperature of 260° C. and a mold temperature of 90° C.). Thereafter,the tests for the physical properties were conducted. The results of themeasurements are shown in Table 2.

Comparative Example 10

In the same manner as in Example 9 without use of any 11-aminoundecanoicacid, there was obtained a composition. The results of the tests for thephysical properties are shown in Table 2.

As will be apparent from Tables 1 and 2, the compositions of theinvention exhibit both good characteristics and good surface properties.In contrast, the compositions of the comparative examples are found tobe inferior in the surface properties.

In order to evidence the excellence of the present invention, theresults of the SEM observation of the section of the compositions areshown in FIGS. 1 to 3. FIG. 1 shows the section of a composition forcomparison which comprises PC (70 wt %) and polypropylene (30 wt %), andFIG. 2 shows the section of a composition comprising PC (70 wt %),maleic anhydride-modified polypropylene (30 wt %) and 11-aminoundecanoicacid (1.8 wt %) FIG. 3 is for a composition comprising PC (70 wt %),epoxy-modified polypropylene (30 wt %) and 11-aminoundecanoic acid (1.8wt % based on the mixture of PC and the modified polypropylene). Thecompositions shown in FIGS. 2 and 3 are inventive ones and aresignificantly smaller in the size of dispersed particles (dispersedparticles=polypropylene-based resin) than that of FIG. 1, revealing thatthe miscibility of the PC with the polypropylene-based resin isimproved.

                                      TABLE 2                                     __________________________________________________________________________                     11-amino          Izod Impact                                                 undeca- Flexural                                                                           Tensile                                                                            Strength                                              Modified.sup.1                                                                      noic    Modulus                                                                            Strength                                                                           (notched)                                                                            HDT                                                                              Peel                             Sample                                                                             PC PP Polyolefin                                                                          acid SEP.sup.2                                                                        (kgf/mm.sup.2)                                                                     (kgf/mm.sup.2)                                                                     (kgf · cm/cm)                                                               (°C.)                                                                     Test                             __________________________________________________________________________    Ex. 4                                                                              80 -- 20    1.8  -- 216  5.2  23     117                                                                              ◯                               (MAH-PP)                                                           5    80 -- 20    1.8  -- 208  5.2  10     117                                                                              ◯                               (Epoxy-PP)                                                         6    80.sup.3                                                                         10 10    0.1  -- 196  4.6  15     126                                                                              ◯                               (Epoxy-PP)                                                         7    50 -- 50    1.8  -- 162  4.0  25     119                                                                              ◯                               (MAH-PP)                                                           8    90 -- 10    1.8  -- 217  5.7  43     125                                                                              ◯                               (MAH-PE)                                                           9    77.5                                                                             -- 17.5  1.8  5  206  4.9  42     112                                                                              ◯                               (MAH-PP)                                                           Com.Ex.4                                                                           80 -- 20    --   -- 186  4.1  33     126                                                                              X                                           (MAH-PP)                                                           5    80.sup.3                                                                         10 10    --   -- 182  4.1  35     124                                                                              X                                           (Epoxy-PP)                                                         6    80.sup.3                                                                         10 10    0.1.sup.4                                                                          -- 198  4.8  5.8    115                                                                              X                                           (Epoxy-PP)                                                         7    80 20 --    0.1  -- 207  5.1  17     113                                                                              X                                8    50 -- 50    1.8  -- 158  4.0  27     117                                                                              X                                           (MAH-PP)                                                           9    90 -- 10    --   -- 219  5.8  23     121                                                                              X                                           (MAH-PE)                                                           10   77.5                                                                             -- 17.5  --   5  201  4.7  38     110                                                                              X                                           (MAH-PP)                                                           __________________________________________________________________________     .sup.1 MAHPP: maleic anhydridemodified polypropylene MAHPE: maleic            anhydridemodified polyethylene EpoxyPP: epoxymodified polypropylene           .sup.2 StyreneEthylene-Propylene copolymer                                    .sup.3 10 wt % of PC was premixed with 11aminoundecanoic acid. The            resultant mixture and other components were then mixed.                       .sup.4 Stearic acid was mixed instead of 11aminoundecanoic acid.         

2! The invention is further described by way of examples with respect toa method for producing a polycarbonate/polyolefin based resincomposition according to the second aspect of the invention. Thestarting materials and evaluation methods used in these examples areshown below. The other starting materials are described above.

Starting Materials

(B) Polyethylene

Linear low density polyethylene (LLDPE)

Linirex AM0710 (MI=0.3) made by Nippon Petrochemicals Co., Ltd.)

(C) Modified polyolefins

Maleic anhydride-modified linear Low density polyethylene,

Admer NB550, made by Mitsui Petrochemical Industries, Ltd.

Maleic anhydride-modified ethylene-propylene block copolymer, C-800X,made by Tonen Corporation Melt kneading

A twin-screw extruder (TEX30HSST) mnade by The Japan Steel Works, Ltd.,was used at an output rate of 10 kg/hour.

Injection molding

An injection molding machine, SAV-60-52, made by Sanjo Seiki Co., Ltd.,was used and the injection molding was effected at a molding temperatureof 260° C. Measurement of characteristic properties

Example 10

4 kg of maleic anhydride-modified polypropylene (AP590P of MitsubishiKasei Corp.) and 40.2 g of 11-aminoundecanoic acid were pre-mixed in aHenschel mixer, followed by melt kneading by means of a twin-screwextruder (L/D=42) at a barrel temperature of 260° C. The resultantpellets were dried in vacuum at 80° C. for 16 hours, part of which waspurified with hot xylene and acetone and shaped into a film by means ofa hot press, followed by subjecting to IR spectral analysis. As aresult, it was found that the peak (at 1784 cm-1) derived from themaleic anhydride disappeared but the peak (170cm-1) derived from thecarboxyl group of the 11-aminoundecanoic acid freshly appeared. Thisreveals that the 11-aminoundecanoic acid is chemically bonded to themaleic anhydride-modified polypropylene.

1.2 kg of the 11-aminoundecanoic acid-modified maleic anhydride-modifiedpolypropylene and 1.8 kg of polycarbonate (Caribre 200-4 of SumitomoDow), which had been dried at 120° C. or 8 hours, were sufficientlypremixed (PC 70 wt %, modifies polypropyrene 30 wt %) by means of theHenschel mixer, followed by melt kneading by means of a twin-screwextruder at a barrel temperature of 300° C. The strand obtained by theextrusion molding was made thinner by use of a microtome and dyed withRuO₄, followed by observation through a transmission-type electronmicroscope. The electron microphotograph is shown in FIG. 4. Theresultant resin composition was subjected to injection molding (at acylinder temperature of 260° C. and a mold temperature of 90° C.) toobtain a molding, followed by subjecting to measurements so mechanicalstrength, heat resistance and the like. The results are shown in Table3.

Example 11

The general procedure of Example 10 was repeated except thatepoxy-modified polypropylene (modified C-900X of Tonen Corp.) was usedinstead of the maleic anhydride-modified polypropylene) and 1.2 kg ofthe 11-aminoundecanoic acid-modified epoxi-modified polypropylene wasused. The results are shown in Table 3.

Example 12

The general procedure of Example 10 was repeated except that maleicanhydride-modified ethylene-propylene block copolymer (C-800X of TonenCorp.) was used instead of the maleic anhydride-modified polypropylene.The results are shown in Table 3.

Example 13

The general procedure of Example 10 was repeated except that maleicanhydride-modified linear low density polyethylene (Admer NB550 ofMitsui Petrochemical Industries Co., Ltd.) was used instead of themaleic anhydride-modified polypropylene. The results are shown in Table3.

Comparative Example 11

In the same manner as in Example 10 without use of any11-aminoundecanoic acid, 1.2 kg of maleic anhydride-modifiedpolypropylene was used with 1.8 kg of polycarbonate, there was obtaineda resin composition. The state of the dispersed particles in a strand isshown in a photograph of FIG. 5 and the mechanical characteristics andheat resistance of the injection molding sample are shown in Table 3.

Comparative Example 12

In the same manner as in Example 11 without use of any11-aminoundecanoic acid, there was obtained a resin composition. Themechanical characteristics and heat resistance of the injection moldingsample are shown in Table 3.

Comparative Example 13

In the same manner as in Example 12 without use of any11-aminoundecanoic acid, there was obtained a resin composition. Themechanical characteristics and heat resistance of the injection moldingsample are shown in Table 3.

Comparative Example 14

In the same manner as in Example 13 without use of any11-aminoundecanoic acid, there was obtained a resin composition. Themechanical characteristics and heat resistance of the injection moldingsample are shown in Table 3.

Example 14

The general procedure of Example 10 was repeated except that 0.15 kg of11-aminoundecanoic acid-modified polypropylene and 2.85 kg ofpolycarbonate were used. The results of the measurements of the physicalproperties are shown in Table 4.

Example 15

The general procedure of Example 10 was repeated except that 0.30 kg of11-aminoundecanoic acid-modified polypropylene and 2.70 kg ofpolycarbonate were used. The results of the measurements of the physicalproperties are shown in Table 4.

Example 16

The general procedure of Example 10 was repeated except that 0.60 kg ofthe 11-aminoundecanoic acid-modified polypropylene and 2.40 kg of thepolycarbonate were used, respectively. The results of measurements ofthe physical properties are shown in Table 4.

Example 17

The general procedure of Example 13 was repeated except that 0.09 kg ofthe 11-aminoundecanoic acid-modified linear low density polyethylene and2.91 kg of the polycarbonate were uses, respectively. The results ofmeasurements of the physical properties are shown in Table 4.

Example 18

The general procedure of Example 13 was repeated except that 0.15 kg ofthe 11-aminoundecanoic acid-modified linear low density polyethylene and2.85 kg of the polycarbonate were used, respectively. The results ofmeasurements of the physical properties are shown in Table 4.

Example 19

The general procedure of Example 13 was repeated except that 0.21 kg ofthe 11-aminoundecanoic acid-modified linear low density polyethylene and2.79 kg of the polycarbonate were used, respectively. The results ofmeasurements of the physical properties are shown in Table 4.

Example 20

The general procedure of Example 13 was repeated except that 0.30 kg ofthe 11-aminoundecanoic acid-modified linear low density polyethylene and2.70 kg of the polycarbonate were used, respectively. The results ofmeasurements of the physical properties are shown in Table 4.

Example 21

The general procedure of Example 16 was repeated except that 0.30 kg ofpolypropylene (Noblen W101 of Sumitomo Chemical Co., Ltd.) and 0.3 kg ofthe 11-aminoundecanoic aced-modified polypropylene were used. Theresults of measurements of the physical properties are shown in Table 4.

Example 22

The general procedure of Example 13 was repeated except that 0.60 kg of11-aminoundecanoic acid-modified linear low density polyethylene and 0.6kg of non-modified linear low density polyethylene (Linirex AM0710 ofNippon Petrochemicals Co., Ltd.) were used. The results of measurementsof the physical properties are shown in Table 4.

Example 23

The general procedure of Example 10 was repeated except thatpolycarbonate having an MI value of 20 (Caribre 200-20 of Sumitomo Dow)was used. The results are shown in Table 4.

Comparative Example 15

The general procedure of Example 16 was repeated without addition of any11-aminoundecanoic acid, thereby obtaining a composition. The results ofmeasurements of the physical properties are shown in Table 4.

Comparative Example 16

The general procedure of Example 20 was repeated without addition of any11-aminoundecanoic acid, thereby obtaining a composition. The results ofmeasurements of the physical properties are shown in Table 4.

                  TABLE 3                                                         ______________________________________                                                                            Izod Impact                                                   Tensile  Flexural                                                                             Strength                                  Peel        HDT     Strength Strength                                                                             (notched)                                 Test        (°C.)                                                                          (kgf/mm.sup.2)                                                                         (kgf/mm.sup.2)                                                                       (kgf · cm/cm)                    ______________________________________                                        Ex.                                                                           10     Δ  123.7   5.14   7.59   14.3                                    11     Δ  125.7   5.10   7.39   25.8                                    12     Δ  124.4   5.03   6.98   28.3                                    13     Δ  116.7   4.75   5.42   58.7                                    Com. Ex.                                                                      11     X        120.7   4.19   6.39   18.3                                    12     X        119.3   4.30   6.54   30.8                                    13     X        118.3   4.51   6.34   27.5                                    14     X        109.3   4.50   5.01   38.7                                    ______________________________________                                    

                  TABLE 4                                                         ______________________________________                                                                            Izod Impact                                                   Tensile  Flexural                                                                             Strength                                  Peel        HDT     Strength Strength                                                                             (notched)                                 Test        (°C.)                                                                          (kgf/mm.sup.2)                                                                         (kgf/mm.sup.2)                                                                       (kgf · cm/cm)                    ______________________________________                                        Ex.                                                                           14     ◯                                                                          138.0   5.91   8.49   86.6                                    15     ◯                                                                          134.4   5.41   8.28   86.5                                    16     ◯                                                                          128.5   5.30   7.96   81.4                                    17     ◯                                                                          140.6   5.97   8.46   90.6                                    18     ◯                                                                          138.7   5.90   8.16   84.1                                    19     ◯                                                                          134.7   5.49   7.71   46.2                                    20     ◯                                                                          131.7   5.34   7.29   25.1                                    21     Δ  126.7   5.23   7.65   82.1                                    22     Δ  118.1   4.72   5.28   59.2                                    23     Δ  123.7   5.08   7.43   12.8                                    Com. Ex.                                                                      15     X        126.5   4.90   7.54   47.2                                    16     X        128.9   5.21   7.19   20.3                                    ______________________________________                                    

As will be apparent from Tables 3 and 4, the PC/polyolefin compositionsobtained according to the process of the invention has both goodmiscibility and good mechanical strength and heat resistance. Incontrast, the compositions of the comparative examples are inferior inthe surface properties.

In order to confirm the excellent effect of the invention, the strandsobtained after the extrusion molding were, respectively, made thin bymeans of a microtome, dyed with RuO₄ and observed through atransmission-type electron microscope. The electron microphotographs areshown in FIGS. 4 (Example 10) and 5 (Comparative Example 11),respectively. While the PC/polyolefin composition obtained according tothe process of the invention (the photograph of FIG. 4) has fineparticles dispersed therein, the composition (the phonograph of FIG. 5)obtained by the simple blending without use of the process of theinvention has larger-size dispersed particles. This reveals than theprocess of the invention contributes to improved miscibility.

3! The molded articles of the resin compositions having good wearproperties according to the third aspect of the invention, which shouldnot be construed as limiting the invention thereto. In these examples,the following abbreviations are used. The other starting materials aredescribed above.

PC: polycarbonate

LDPE: low density polyethylene

LLDPE: linear low density polyethylene

HDPE: high density polyethylene

PTFE: polytetrafluoroethylene

Starting materials used

(B) Polyethylene resins

Linirex AM0710 (LLDPE with a melt index of 0.3) of Nippon PetrochemicalsCo., Ltd.

Stafron E703 (HDPE with a melt index of 0.3) of Nippon PetrochemicalsCo., Ltd.

Rexron M14 (LDPE with a melt index of 0.3) of Nippon Petrochemicals Co.,Ltd.

(C) Modified polyethylene resins

Admer NB550 (maleic anhydride-modified LLDPE with a melt index of 0.9and an amount of modification of 0.14%*) of Mitsui Petrochemicals Co.,Ltd.

Admer NF510 (maleic anhydride-modified LLDPE with a melt index of 1.8and an amount of modification of 0.07%*) of Mitsui Petrochemicals Co.,Ltd.

Admer NF505 (maleic anhydride-modified LLDPE with a melt index of 3.5and an amount of modification of 0.09%*) of Mitsui Petrochemicals Co.,Ltd.

Admer NF550 (maleic anhydride-modified LLDPE with a melt index of 6.5and an amount of modification of 0.26%*) of Mitsui Petrochemicals Co.,Ltd.

Admer HB550 (maleic anhydride-modified HDPE with a melt index of 0.2 andan amount of modification of 0.07%*) of Mitsui Petrochemicals Co., Ltd.

Admer LF300 (maleic anhydride-modified LDPE with a melt index of 1.2 andan amount of modification of 0.09%*) of Mitsui Petrochemicals Co., Ltd.

*) The amount of modification was quantitatively determined according toIR spectra.

(D) HOOC--R--NH₂

11-aminoundecanoic acid, 6-aminocaproic acid, p-aminobenzoic acid (allmade by Aldrich)

Melt kneading

A twin-screw extruder (TEX30HSST) made by The Japan Steel Works, Ltd.,was used for kneading at 260° C. or 300° C. at an output rate of 10kg/hour.

Injection molding

An injection molding machine, SAV-60-52, made by Sanjo Seiki Co., Ltd.,was used. The injection molding was effected under conditions of acylinder temperature of 260° C., an injection pressure of 50 kg/cm², aninjection rate of 50% and a mold temperature of 100° C. for pieces forbending and tensile tests and under conditions of a cylinder temperatureof 290° C., an injection pressure of 70 kg/cm², an injection rate of 50%and a mold temperature of 100° C. for a ring-shaped piece for wear test.Measurement of physical properties

(1) Wear test: a ring-shaped molding was molded and was subjected to awear test using a counterpart having a similar shape (made of a steel(S-45C) ). The conditions of a ring-on-ring method included a linearvelocity of 30 m/minute, a load of 2.6 kg/cm² and a test time of 72hours. The torque at the time of the wear test was detected with a loadcell, from which a coefficient of dynamic friction was calculated. Aspecific abrasion loss was determined from a variation in weight priorto and after the wear test. Some samples were subjected to measurementof a linear abrasion loss thereof as a function of time under conditionswhere a laser displacement detector was attached to a wear tester.

(2) Observation of morphology

A thin film with a thickness of approximately 900 angstroms was takenfrom a ring-shaped test piece at a section near the sliding surface byuse of a microtome, followed by dyeing with RuO₄ and observation througha transmission electron microscope. An average aspect ratio wascalculated by measuring aspect ratios of arbitrarily selected 100particles from the resultant electron microphotograph and calculating anaverage of the 100 measurements. The other measurements of thecharacteristic properties were used the same methods as alreadydescribed.

Example 24

5 kg of maleic anhydride-modified linear low density polyethylene (AdmerNB550) and 50.5 g of 11-aminoundecanoic acid were sufficiently mixed ina Henschel mixer, followed by melt kneading at 260° C. by use of atwin-screw extruder. The resultant mixture was dried in vacuum at 80° C.for 12 hours, after which 0.3 kg of the mixture and 9.7 kg ofpolycarbonate (MI=4) were mixed in the Henschel ratio followed by meltkneading at 300° C. by use of the twin-screw extruder. The resultantmixture was dried at 120° C. for 8 hours and injection molded, followedby measurements of physical properties. The results are shown in Table5. The transmission-type electron microscope photograph of a section inthe vicinity of the sliding surface of a ring-shaped test piece is shownas Photograph A of FIG. 6.

Comparative Example 17

The general procedure of Example 24 was repeated except that linear lowdensity polyethylene (Linirex AM0710) was used instead of the maleicanhydride-modified linear low density polyethylene (Admer NB550) andthat 11-aminoundecanoic acid was not added. The results are shown inTable 5 with a transmission-type electron microscope photograph shown asPhotograph B of FIG. 6.

Example 25

5 kg of maleic anhydride-modified linear low density polyethylene (AdmerN3530) and 50.5 g of 11-aninoundecanoic acid were sufficiently mixed ina Henschel mixer, follower by melt kneading at 260° C. by use of atwin-screw extruder The resultant mixture was dried in vacuum at 80° C.for 12 hours, after which 0.5 kg of the mixture and 9.5 kg ofpolycarbonate (MI=4) were mixed in the Henschel mixer, followed by meltkneading at 300° C. by use of the twin-screw extruder. The resultantmixture was dried at 120° C. for 8 hours and injection molded, followedby measurements of physical properties. The results are shown in Table5.

Example 26

5 kg of maleic anhydride-modified linear low density polyethylene (AdmerNB550) and 50.5 g of 11-aminoundecanoic acid were sufficiently mixed ina Henschel mixer, followed by melt kneading at 260° C. by use of atwin-screw extruder. The resultant mixture was dried in vacuum at 80° C.for 12 hours, after which 1.0 kg of the mixture and 9.0 kg ofpolycarbonate (MI=4) were mixed in the Henschel mixer, followed by meltkneading at 300° C. by use of the twin-screw extruder. The resultantmixture was dried at 120° C. for 8 hours and injection molded, followedby measurements of physical properties. The results are shown in Table5.

Example 27

5 kg of maleic anhydride-modified linear low density polyethylene (AdmerNF510) and 50.5 g of 11-aminoundecanoic acid were sufficiently mixed ina Henschel mixer, followed by melt kneading at 260° C. by use of atwin-screw extruder. The resultant mixture was dried in vacuum at 80° C.for 12 hours, after which 0.5 kg of the mixture and 9.5 kg ofpolycarbonate (MI=4) were mixed in the Henschel mixer, followed by meltkneading at 300° C. by use of the twin-screw extruder. The resultantmixture was dried at 120° C. for 8 hours and injection molded, followedby measurements of physical properties. The results are shown in Table5.

Example 28

5 kg of maleic anhydride-modified linear low density polyethylene (AdmerNF505) and 50.5 g of 11-aminoundecanoic acid were sufficiently mixed ina Henschel mixer, followed by melt kneading at 260° C. by use of atwin-screw extruder. The resultant mixture was dried in vacuum a. 80° C.for 12 hours, after which 0.5 kg of the mixture and 9.5 kg ofpolycarbonate (MI=4) were mixed in the Henschel mixer, followed by meltkneading at 300° C. by use of the twin-screw extruder. The resultantmixture was dried at 120° C. for 8 hours and injection molded, followedby measurements of physical properties. The results are shown in Table5.

Example 29

5 kg of maleic anhydride-modified linear low density polyethylene (AdmerNF550) and 50.5 g of 11-aminoundecanoic acid were sufficiently mixed ina Henschel mixer, followed by melt kneading at 260° C. by use of atwin-screw extruder. The resultant mixture was dried in vacuum at 80° C.for 12 hours, after which 0.5 kg of the mixture and 9.5 kg orpolycarbonate (MI=4) were mixed in the Henschel mixer, followed by meltkneading at 300° C. by, use of the twin-screw extruder. The resultantmixture was dried at 120° C. for 8 hours and injection molded, followedby measurements of physical properties. The results are shown in Table5.

Example 30

5 kg of maleic anhydride-modified linear low density polyethylene (AdmerNB550) and 50.5 c of 11-aminoundecanoic acid were sufficiently mixed ina Henschel mixer, followed by melt kneading at 260° C. by use of atwin-screw extruder. The resultant mixture was dried in vacuum at 80° C.for 12 hours, after which 0.5 kg of the mixture and 9.5 kg ofpolycarbonate (MI=20) were mixed in the Henschel mixer, followed by meltkneading at 300° C. by use of the twin-screw extruder. The resultantmixture was Dried at 120° C. for 8 hours and injection molded, followedby measurements of physical properties. The results are shown in Table5.

Comparative Example 18

The general procedure of Example 26 was repeated except that linear lowdensity polyethylene (Linirex AM0710) was used instead of the maleicanhydride-modified linear low density polyethylene (Admer NB550) andthat 11-aminoundecanoic acid was not added. The results are shown inTable 5.

Example 31

5 kg of maleic anhydride-modified linear low density polyethylene (AdmerHB500) and 50.5 g of 11-aminoundecanoic acid were sufficiently mixed ina Henschel mixer, followed by melt kneading at 260° C. by use of atwin-screw extruder. The resultant mixture was dried in vacuum at 80° C.for 12 hours, after which 0.5 kg of the mixture and 9 5 kg ofpolycarbonate (MI=4) were mixed in the Henschel mixer, followed by meltkneading at 300° C. by use of the twin-screw extruder. The resultantmixture was dried at 120° C. for 8 hours and injection molded, followedby measurements of physical properties. The results are shown in Table5.

Comparative Example 19

The general procedure of Example 31 was repeated except that highdensity polyethylene (Stafron E703) was used instead of the maleicanhydride-modified linear low density polyethylene (Admer HB500) andthat 11-aminoundecanoic acid was not added. The results are shown inTable 5.

Example 32

5 kg of maleic anhydride-modified low density polyethylene (Admer LF300)and 50.5 g of 11-aminoundecanoic acid were sufficiently mixed in aHenschel mixer, followed by melt kneading at 260° C. by use of atwin-screw extruder. The resultant mixture was dried in vacuum at 80° C.for 12 hours, after which 0.5 kg of the mixture and 9.5 kg ofpolycarbonate (MI=4) were mixed in the Henschel mixer, followed by meltkneading at 300° C. by use of the twin-screw extruder. The resultantmixture was dried at 120° C. for 8 hours and injection molded, followedby measurements of physical properties. The results are shown in Table5.

Comparative Example 20

The general procedure of Example 32 was repeated except that low densitypolyethylene (Rexron 4) was used instead of the maleicanhydride-modified low density polyethylene (Admer LF300) and that11-aminoundecanoic acid was not added. The results are shown in Table 5.

Example 33

The general procedure of Example 25 was repeated using 6-aminocaproicacid In place of 11-aminoundecanoic acid. The results are shown in Table5.

Example 34

The general procedure of Example 25 was repeated using p-aminobenzoicacid instead of 11-aminoundecanoic acid. The results are shown in Table5.

Example 35

0.5 kg of maleic anhydride-modified linear low density polyethylene(Admer NB550), 5.05 g of 11-aminoundecanoic acid and 9.5 kg ofpolycarbonate (MI=4) were sufficiently mixed in a Henschel mixer,followed by melt kneading at 300° C. by use of a twin-screw extruder.The resultant mixture was dried at 80° C. for 12 hours in vacuum,followed by injection molding and measurements of physical properties.The results are shown in Table 5.

As will be apparent from Table 5, the compositions of the invention haveall good mechanical strength, heat resistance and slidingcharacteristics. In contrast, the compositions of the comparativeexamples have been found to be poor in wear properties. It has been alsofound that the compositions of the examples are substantially equal to aknown sliding PC/PTFE material whose characteristic properties areindicated in the table as a reference.

FIG. 7 shows a variation in linear wear loss of each or the compositionsof the examples and the comparative examples and the known PC/PTFEsliding material as a function of time. From this, it will be seen thatthe compositions of the examples are better in the wear characteristic.

Photographs A and B of FIG. 6 are, respectively, electron microscopephotographs showing morphology in the vicinities of the surfaces of thering moldings of Example 24 and Comparative Example 17. From thetransmission type photographs, it will be seen that the dispersionstates are apparently different from each other: with the composition ofthe comparative example, the polyethylene particles elongated in theform of a layer are observed, whereas with the composition of theexample, the polyethylene dispersed particles are observed substantiallyin the form of spheres being dispersed.

                                      TABLE 5                                     __________________________________________________________________________                 Coeffi-                           Average                                     cient of   Tensile Strength/                                                                     Flexural Strength/                                                                    Izod Impact                                                                          Aspect                         Specific     Dy- HDT    Tensile Flexural                                                                              Strength                                                                             Ratio                          Wear Loss    namic                                                                             (°C.,                                                                         Modulus Modulus (notched)                                                                            of PE                          (×10.sup.-15 m.sup.3 /Nm)                                                            Friction                                                                          18.6 kgf/cm.sup.2)                                                                   (kgf/mm.sup.2)                                                                        (kgf/mm.sup.2)                                                                        (kgf · cm/cm)                                                               particles.sup.1                __________________________________________________________________________    Ex. 24                                                                             3.8     0.09                                                                              140.6  5.97/198                                                                              8.46/215                                                                              90.6   1.8                            25   1.4     0.12                                                                              138.7  5.90/195                                                                              8.16/208                                                                              84.1   2.3                            26   0.9     0.15                                                                              136.2  5.87/189                                                                              7.91/201                                                                              79.2   4.5                            27   2.8     0.12                                                                              138.5  5.87/194                                                                              8.06/205                                                                              85.6   2.7                            28   2.5     0.12                                                                              138.7  5.91/196                                                                              8.15/209                                                                              84.3   2.5                            29   1.5     0.13                                                                              137.9  5.89/196                                                                              8.07/207                                                                              84.2   2.6                            30   1.5     0.12                                                                              139.0  5.91/194                                                                              8.21/207                                                                              83.2   2.9                            31   5.4     0.15                                                                              138.6  5.87/193                                                                              8.03/206                                                                              80.3   3.1                            32   2.7     0.16                                                                              137.9  5.68/192                                                                              8.07/209                                                                              78.3   2.8                            33   1.1     0.13                                                                              138.9  5.92/196                                                                              8.21/209                                                                              84.3   3.4                            34   1.8     0.13                                                                              138.9  5.93/196                                                                              8.02/209                                                                              83.6   3.9                            35   1.7     0.13                                                                              139.0  5.94/197                                                                              8.21/210                                                                              55.0   1.9                            Com.Ex.                                                                            56.7    0.09                                                                              136.0  5.77/196                                                                              8.39/207                                                                              62.5   10.3                           17                                                                            18   20.3    0.16                                                                              137.2  5.89/184                                                                              7.94/203                                                                              58.2   10.5                           19   109.3   0.19                                                                              135.2  5.72/189                                                                              8.01/203                                                                              63.5   9.8                            20   25.4    0.17                                                                              136.3  5.84/196                                                                              8.05/204                                                                              63.7   8.9                            PC/PTFE.sup.2                                                                      4.2     0.15                                                                              139.3  4.79/172                                                                              7.04/181                                                                              26.0   --                             __________________________________________________________________________     .sup.1 Average aspect ratio of PE particles dispersed to a depth of 20        μm from the outer surface of strands.                                      .sup.2 Lubriconp DL4030 ® manufactured by LNP Inc. Composition:           PC/PTFE = 85%/15%                                                        

4! The resin compositions and molded articles thereof having a goodsolvent resistance according to the fourth aspect of the invention isfurther described by way of examples, which should not be construed aslimiting the invention thereto. In the examples, the same abbreviationsdescribed above are sometimes used.

Starting materials used

(C) Modified polyolefin resins

Novatec AP590P (maleic anhydride-modified PP with a melt index of 50 andan amount of modification of 0.50%*) of Mitsubishi Kasei Corp.

*) The amount of modification was quantitatively determined from IRspectra.

The other starting materials are described above.

Melt kneading

A twin-screw extruder (TEX30HSST) made by The Japan Steel Works, Ltd.,was used for kneading at 260° C. and 300° C. at an output rate of 10kg/hour.

Injection molding

An injection molding machine, SAV-60-52, made by Sanjo Seiki Co., Ltd.,was used. The injection molding was effected under conditions of acylinder temperature of 260° C., an injection pressure of 50 kg/cm², aninjection rate of 50% and a mold temperature of 100° C.

Measurement of physical properties

(1) Organic solvent resistance test: a test piece for bending test wasimmersed in gasoline, and an increase in weight of the test piece wasmeasured, along with an appearance change through visual observation, asa function of time.

The other measurements of the characteristic properties were used thesame methods as already described.

Example 36

5 kg of maleic anhydride-modified linear low density polyethylene (AdmerNB550) and 50.5 g of 11-aminoundecanoic acid were sufficiently mixed ina Henschel mixer, followed by melt kneading at 260° C. by use of atwin-screw extruder. The resultant mixture was dried in vacuum at 80° C.for 12 hours, after which 0.5 kg of the mixture and 9.5 kg ofpolycarbonate (MI=4) were mixed in the Henschel mixer, followed by meltkneading at 300° C. by use of the twin-screw extruder. The resultantmixture was dried at 120° C. for 8 hours and injection molded, followedby measurements of physical properties. The results are shown in Tables6 and 7 and in FIG. 8.

Comparative Example 21

The general procedure of Example 36 was repeated except that linear lowdensity polyethylene (Linirex AM0710) was used instead of the maleicanhydride-modified linear low density polyethylene (Admer NB550) andthat 11-aminoundecanoic acid was not added. The results are shown inTables 6 and 7 and in FIG. 8.

Example 37

5 kg of maleic anhydride-modified homopolypropylene (AP590P) and 50.5 gof 11-aminoundecanoic acid were sufficiently mixed in a Henschel mixer,followed by melt kneading at 260° C. by use of a twin-screw extruder.The resultant mixture was dried in vacuum at 80° C. for 12 hours, afterwhich 0.5 kg of the mixture and 9.5 kg of polycarbonate (MI=4) weremixed in the Henschel mixer, followed by melt kneading at 300° C. by useof the twin-screw extruder. The resultant mixture was dried at 120° C.for 8 hours and injection molded, followed by measurements of physicalproperties. The results are shown in Tables 6 and 7 and in FIG. 9.

Comparative Example 22

The general procedure of Example 37 was repeated except thathomopolypropylene (Noblen W101) was used instead of the maleicanhydride-modified homopolypropylene (AP590P) and that11-aminoundecanoic acid was not added. The results are shown in Tables 6and 7 and in FIG. 9.

As will be apparent from Tables 6 and 7, the compositions of theinvention have all good mechanical strength and heat resistance alsogood organic solvent resistance. In contrast, the compositions of thecomparative examples and polycarbonate are poor particularly in theorganic solvent resistance. The compositions of the examples haveorganic solvent resistance and mechanical strength equal to or greaterthan a known PC/PET composition which is shown as a reference.

FIG. 8 shows an increase in weight of the composition of Example 36 ingasoline, the composition of Comparative example 21 and known PC/PETcompositions for comparison. The composition of the example is smallerin the increase than the PC and the composition of the comparativeexample and thus is better in the organic solvent resistance.

Photographs FIG. 10A to FIG. 10F are those photographs of test piecesurfaces (×6.5) observed after immersion in gasoline for 1320 minutes ofthe test pieces of the compositions of the examples (36, 37),comparative examples (21, 22), PC and PC/PET. Although the compositionsof the comparative examples and polycarbonate had fine cracks observedin the surfaces, no crack was observed for the compositions of theexamples. Thus, little variation in appearance of the examples in theorganic solvent was found.

                  TABLE 6                                                         ______________________________________                                        HDT                           Izod                                            (°C.,     Tensile        Flexural                                                                            Impact                                  18.6    Tensile      Mod-  Flexural Mod-  Strength                            kgf/    Strength                                                                              /    ulus  Strength                                                                            /  ulus  (notched)                           cm.sup.2)                                                                             (kgf/mm.sup.2)                                                                             (kgf/mm.sup.2)                                                                             (kgf · cm/cm)                      ______________________________________                                        Ex.                                                                           36   138.7  5.90    /  195   8.16  /  208   84.1                              37   137.1  5.86    /  194   8.21  /  208   82.5                              Com.                                                                          Ex.                                                                           21   136.0  5.77    /  196   8.39  /  207   62.5                              22   135.1  5.69    /  197   8.42  /  207   61.3                              PC   134.0  6.30    /  --    9.80  /  242   75.0                              PC/  125.0  6.40    /  205   9.30  /  228   15.0                              PET                                                                           ______________________________________                                    

                  TABLE 7                                                         ______________________________________                                        Immersion        Sample                                                       Time                         Ex. Com. Ex.                                                                             Ex. Com. Ex.                          (min.) Appearance                                                                              PC    PC/PET                                                                              36  21     37  22                                ______________________________________                                        0      Crack.sup.1)                                                                            ◯                                                                       ◯                                                                       ◯                                                                     ◯                                                                        ◯                                                                     ◯                            Turbidity.sup.2)                                                                        ◯                                                                       --    --  --     --  --                                       Gloss.sup.3)                                                                            ◯                                                                       ◯                                                                       ◯                                                                     ◯                                                                        ◯                                                                     ◯                     30     Crack     Δ                                                                             ◯                                                                       ◯                                                                     ◯                                                                        ◯                                                                     ◯                            Turbidity X     --    --  --     --  --                                       Gloss     X     ◯                                                                       ◯                                                                     Δ                                                                              ◯                                                                     ◯                     150    Crack     Δ                                                                             ◯                                                                       ◯                                                                     ◯                                                                        ◯                                                                     Δ                                  Turbidity X     --    --  --     --  --                                       Gloss     X     ◯                                                                       ◯                                                                     Δ                                                                              ◯                                                                     Δ                           330    Crack     Δ                                                                             ◯                                                                       ◯                                                                     X      ◯                                                                     X                                        Turbidity X     --    --  --     --  --                                       Gloss     X     Δ                                                                             Δ                                                                           X      Δ                                                                           --                                720    Crack     Δ                                                                             ◯                                                                       ◯                                                                     X      ◯                                                                     X                                        Turbidity X     --    --  --     --  --                                       Gloss     X     Δ                                                                             Δ                                                                           X      Δ                                                                           X                                 1320   Crack     X     ◯                                                                       ◯                                                                     X      ◯                                                                     X                                        Turbidity X     --    --  --     --  --                                       Gloss     X     Δ                                                                             Δ                                                                           X      Δ                                                                           --                                ______________________________________                                         .sup.1) Presence or cracks: ◯; none, Δ; slight, X;          considerable                                                                  .sup.2) Turbidity: ◯; none, Δ; slight, X; considerable      .sup.3) Gloss: ◯; not changed, Δ; slightly changed, X;      changed                                                                  

5! The glass fiber reinforced resin compositions according to the fifthaspect of the invention is further described in more detail, whichshould not be construed as limiting the invention thereto. The meltkneading and injection molding were conducted in the following mannerand various physical properties were measured according to the followingmethods.

Starting materials used are described above.

Melt kneading

A twin-screw extruder (TEX30HSST, made by The Japan Steel Works, Ltd.)was used for kneading at 260° C. or 300° C. at an output rate of 10kg/hour.

Injection molding

An injection molding machine (SAV-60-52 made by Sanjo Seiki Co., Ltd.)was used. The injection molding was effected under conditions of acylinder temperature of 260° C., an injection pressure of 50 kg/cm², aninjection rate of 50% and a mold temperature of 100° C. for bending andtensile test pieces and under conditions of a cylinder temperature of290° C., an injection pressure of 70 kg/cm², an injection rate of 50%and a mold temperature of 100° C. for a ring-shaped piece for wear test.

Measurement of physical properties are described above.

Example 38

5 kg of maleic anhydride-modified linear low density polyethylene (AdmerNB550) and 50.5 g of 11-aminoundecanoic acid were sufficiently mixed ina Henschel mixer, followed by melt kneading at 260° C. by use of atwin-screw extruder. The resultant mixture was dried in vacuum at 80° C.for 12 hours, after which 0.3 kg of the mixture and 9.7 kg ofpolycarbonate (MI=4 g/10 minutes) were mixed in the Henschel mixer,followed by melt kneading at 300° C. by use of the twin-screw extruder.The resultant mixture was dried at 120° C. for 8 hours to obtain apolycarbonate resin composition. 3.5 kg of the polycarbonate resincomposition and 1.5 kg of glass fibers (having a fiber length of 3 mmand a diameter of the fiber of 9 μm and treated with an aminosilane)were sufficiently mixed by means of the Henschel mixer, followed bykneading at 260° C. by means of the twin-screw extruder to obtain aglass fiber-reinforced polycarbonate resin composition comprised of 70parts by weight of the polycarbonate resin composition and 30 parts byweight of the glass fibers. The glass fiber-reinforced polycarbonateresin composition was subjected to injection molding to provide testpieces. The test pieces were subjected to measurements of bendingstrength, modulus of elasticity, impact strength and thermal deformationtemperature and also to a wear test. The results are shown in Table 8.

Comparative Example 23

The general procedure of Example 38 was repeated except that linear lowdensity polyethylene (Linirex AM0710) was used instead of maleicanhydride-modified linear low density polyethylene (Admer NB550) andthat 11-aminoundecanoic acid was not added, thereby obtaining a glassfiber-containing composition. The thus obtained composition wassubjected to injection molding to obtain test pieces, followed bymeasurements of bending strength, modulus of elasticity, impact strengthand thermal deformation temperature and also by a wear test. The resultsare shown in Table 8.

Example 39

5 kg of maleic anhydride-modified linear low density polyethylene (AdmerNB550) and 50.5 g of 11-aminoundecanoic acid were sufficiently mixed ina Henschel mixer, followed by melt kneading at 260° C. by use of atwin-screw extruder. The resultant mixture was dried in vacuum at 80° C.for 12 hours, after which 0.5 kg of the mixture and 9.5 kg ofpolycarbonate (MI=4 g/10 minutes) were mixed in the Henschel mixer,followed by melt kneading at 300° C. by use of the twin-screw extruder.The resultant mixture was dried at 120° C. for 8 hours to obtain apolycarbonate resin composition. 3.5 kg of the polycarbonate resincomposition and 1.5 kg of glass fibers (having a fiber length of 3 mmand a diameter of the fiber of 9 μm and treated with an aminosilane)were sufficiently mixed by means of the Henschel mixer, followed bykneading at 260° C. by means of the twin-screw extruder to obtain aglass fiber-reinforced polycarbonate resin composition comprised of 70parts by weight of the polycarbonate resin composition and 30 parts byweight of the glass fibers. The glass fiber-reinforced polycarbonateresin composition was subjected to injection molding to provide testpieces. The test pieces were subjected to measurements of bendingstrength, modulus of elasticity, impact strength and thermal deformationtemperature and also to a wear test. The results are shown in Table 8.

Example 40

5 kg of maleic anhydride-modified linear low density polyethylene (AdmerNB550) and 50.5 g of 11-aminoundecanoic acid were sufficiently mixed ina Henschel mixer, followed by melt kneading at 260° C. by use of atwin-screw extruder. The resultant mixture was dried in vacuum at 80° C.for 12 hours, after which 1.0 kg of the mixture and 9.0 kg ofpolycarbonate (MI=4 g/10 minutes) where mixed in the Henschel mixer,followed by melt kneading at 300° C. by use of the twin-screw extruderto obtain a polycarbonate resin composition. The polycarbonate resincomposition was dried at 120° C. for 8 hours. 3.5 kg of thepolycarbonate resin composition and 1.5 kg of glass fibers (having afiber length of 3 mm and a diameter of the fiber of 9 μm and treatedwith an aminosilane) were sufficiently mixed by means of the Henschelmixer, followed by kneading at 260° C. by means of a twin-screw extruderto obtain a glass fiber-reinforced polycarbonate resin compositioncomprised of 70 parts by weight of the polycarbonate resin compositionand 30 parts by weight of the glass fibers. The glass fiber-reinforcedpolycarbonate resin composition was subjected to injection molding toprovide test pieces. The test pieces were subjected to measurements ofbending strength, modulus of elasticity, impact strength and thermaldeformation temperature and also to a wear test. The results are shownin Table 8.

Example 41

5 kg of maleic anhydride-modified linear low density polyethylene (AdmerNF510) and 50.5 g of 11-aminoundecanoic acid were sufficiently mixed ina Henschel mixer, followed by melt kneading at 260° C. by use of atwin-screw extruder. The resultant mixture was dried in vacuum at 80° C.for 12 hours, after which 0.5 kg of the mixture and 9.5 kg ofpolycarbonate (MI=4 g/10 minutes) were mixed in the Henschel mixer,followed by melt kneading at 300° C. by use of the twin-screw extruderto obtain a polycarbonate resin composition. The polycarbonate resincomposition was dried at 120° C. for 8 hours. 3.5 kg of thepolycarbonate resin composition and 1.5 kg of class fibers (having afiber length of 3 mm and a diameter of the fiber of 9 μm and treatedwith an aminosilane) were sufficiently mixed by means of the Henschelmixer, followed by kneading at 260° C. by means of the twin-screwextruder to obtain a class fiber-reinforced polycarbonate resincomposition comprised of 70 parts by weight of the polycarbonate resincomposition and 30 parts by weight of the glass fibers. The glassfiber-reinforced polycarbonate resin composition was subjected toinjection molding to provide test pieces. The test pieces were subjectedto measurements of bending strength, modulus of elasticity, impactstrength and thermal deformation temperature and also to a wear test.The results are shown in Table 8.

Example 42

5 kg of maleic anhydride-modified linear low density polyethylene (AdmerNF505) and 50.5 g of 11-aminoundecanoic acid were sufficiently mixed ina Henschel mixer, followed by melt kneading at 260° C. by use of atwin-screw extruder. The resultant mixture was dried in vacuum at 80° C.for 12 hours, after which 0.5 kg of the mixture and 9.5 kg ofpolycarbonate (MI=4 g/10 minutes) were mixed in the Henschel mixer,followed by melt kneading at 300° C. by use of the twin-screw extruderto obtain a polycarbonate resin composition. The polycarbonate resincomposition was dried at 120° C. for 8 hours. 3.5 kg of thepolycarbonate resin composition and 1.5 kg of glass fibers (having afiber length of 3 mm and a diameter of the fiber of 9 μm and treatedwith an aminosilane) were sufficiently mixed by means of the Henschelmixer, followed by kneading at 260° C. by means of the twin-screwextruder to obtain a glass fiber-reinforced polycarbonate resincomposition comprised of 70 parts by weight of the polycarbonate resincomposition and 30 parts by weight of the glass fibers. The glassfiber-reinforced polycarbonate resin composition was subjected toinjection molding to provide test pieces. The test pieces were subjectedto measurements of bending strength, modulus of elasticity, impactstrength and thermal deformation temperature and also to a wear test.The results are shown in Table 8.

Example 43

5 kg of maleic anhydride-modified linear low density polyethylene (AdmerNF550) and 50.5 g of 11-aminoundecanoic acid were sufficiently mixed ina Henschel mixer, followed by melt kneading at 260° C. by use of atwin-screw extruder. The resultant mixture was dried in vacuum at 80° C.for 12 hours, after which 0.5 kg of the mixture and 9.5 kg ofpolycarbonate (MI=4 g/10 minutes) were mixed in the Henschel mixer,followed by melt kneading at 300° C. by use of the twin-screw extruderto obtain a polycarbonate resin composition. The polycarbonate resincomposition was dried at 120° C. for 8 hours. 3.5 kg of thepolycarbonate resin composition and 1.5 kg of glass fibers (having afiber length of 3 mm and a diameter of the fiber of 9 μm and treatedwith an aminosilane) were sufficiently mixed by means of the Henschelmixer, followed by kneading at 260° C. by means of She twin-screwextruder to obtain a glass fiber-reinforced polycarbonate resincomposition comprised of 70 parts by weight of the polycarbonate resincomposition and 30 parts by weight of the glass fibers. The glassfiber-reinforced polycarbonate resin composition was subjected toinjection molding to provide rest pieces. The test pieces were subjectedto measurements of bending strength, modulus of elasticity, impactstrength and thermal deformation temperature.and also to a wear test.The results are shown in Table 8.

Example 44

5 kg of maleic anhydride-modified linear low density polyethylene (AdmerNB550) and 50.5 g of 11-aminoundecanoic acid were sufficiently mixed ina Henschel mixer, followed by melt kneading at 260° C. by use of atwin-screw extruder. The resultant mixture was dried in vacuum at 80° C.for 12 hours, after which 0.5 kg of the mixture and 9.5 kg ofpolycarbonate (MI=20 g/10 minutes) were mixed in the Henschel mixer,followed by melt kneading at 300° C. by use of the twin-screw extruderto obtain a polycarbonate resin composition. The polycarbonate resincomposition was dried at 120° C. for 8 hours. 3.5 kg of thepolycarbonate resin composition and 1.5 kg of glass fibers (having afiber length of 3 mm. and a diameter of the fiber of 9 μm and treatedwith an aminosilane) were sufficiently mixed by means of the Henschelmixer, followed by kneading at 260° C. by means of the twin-screwextruder to obtain a glass fiber-reinforced polycarbonate resincomposition comprised of 70 parts by weigh of the polycarbonate resincomposition and 30 parts by weight of the glass fibers. The glassfiber-reinforced polycarbonate resin composition was subjected toinjection molding to provide test pieces. The test pieces were subjectedto measurements of bending strength, modulus of elasticity, impactstrength and thermal deformation temperature and also to a wear test.The results are shown in Table 8.

Comparative Example 24

The general procedure of Example 40 was repeated except that linear lowdensity polyethylene (Linirex A0710) was used instead of the maleicanhydride-modified linear low density polyethylene (Admer NB550) andthat 11-aminoundecanoic acid was not added, thereby obtaining a glassfiber-containing composition. The thus obtained composition wassubjected to injection molding to obtain test pieces, followed bymeasurements of bending strength, modulus of elasticity, impact strengthand thermal deformation temperature and also by a wear test. The resultsare shown in Table 8.

Example 45

5 kg of maleic anhydride-modified high density polyethylene (AdmerHB500) and 50.5 g of 11-aminoundecanoic acid were sufficiently mixed ina Henschel mixer, followed by melt kneading at 260° C. by use of atwin-screw extruder. The resultant mixture was dried in vacuum at 80° C.for 12 hours, after which 0.5 kg of the mixture and 9.5 kg ofpolycarbonate (MI=4) were mixed in the Henschel mixer, followed by meltkneading at 300° C. by use of the twin-screw extruder to obtain apolycarbonate resin composition. The polycarbonate resin composition wasdried at 120° C. for 8 hours. 3.5 kg of the polycarbonate resincomposition and 1.5 kg of glass fibers (having a fiber length of 3 mmand a diameter of the fiber of 9 μm and treated with an aminosilane)were sufficiently mixed by means of the Henschel mixer, followed bykneading at 260° C. by means of the twin-screw extruder to obtain aglass fiber-reinforced polycarbonate resin composition comprised of 70parts by weight of the polycarbonate resin composition and 30 parts byweight of the glass fibers. The glass fiber-reinforced polycarbonateresin composition was subjected to injection molding to provide testpieces. The test pieces were subjected to measurements of bendingstrength, modulus of elasticity, impact strength and thermal deformationtemperature and also to a wear test. The results are shown in Table 8.

Comparative Example 25

The general procedure of Example 45 was repeated except that highdensity polyethylene (Stafron E703) was used instead of the maleicanhydride-modified high density polyethylene (Admer NB500) and that11-aminoundecanoic acid was not added, thereby obtaining a glassfiber-containing composition. The thus obtained composition wassubjected to injection molding to obtain test pieces, followed bymeasurements of bending strength, modulus of elasticity, impact strengthand thermal deformation temperature and also by a wear test. The resultsare shown in Table 8.

Example 46

5 kg of maleic anhydride-modified low density polyethylene (Admer LF300)and 50.5 g of 11-aminoundecanoic acid were sufficiently mixed in aHenschel mixer, followed by melt kneading at 260° C. by use of atwin-screw extruder. The resultant mixture was dried in vacuum at 80° C.for 12 hours, after which 0.5 kg of the mixture and 9.5 kg ofpolycarbonate (MI=4) were mixed in the Henschel mixer, followed by meltkneading at 300° C. by use of the twin-screw extruder to obtain apolycarbonate resin composition. The polycarbonate resin composition wasdried at 120° C. for 8 hours. 3.5 kg of the polycarbonate resincomposition and 1.5 kg of glass fibers (having a fiber length of 3 mmand a diameter of the fiber of 9 μm and treated with an aminosilane)were sufficiently mixed by means of the Henschel mixer, followed bykneading at 260° C. by means of the twin-screw extruder to obtain aglass fiber-reinforced polycarbonate resin composition comprised of 70parts by weight of the polycarbonate resin composition and 30 parts byweight of the glass fibers. The glass fiber-reinforced polycarbonateresin composition was subjected to injection molding to provide testpieces. The test pieces were subjected to measurements of bendingstrength, modulus of elasticity, impact strength and thermal deformationtemperature and also to a wear test. The results are shown in Table 8.

Comparative Example 26

The general procedure of Example 46 was repeated except that low densitypolyethylene (Rexron M14) was used instead of the maleicanhydride-modified low density polyethylene (Admer LF300) and that11-aminoundecanoic acid was not added, thereby obtaining a glassfiber-containing composition. The thus obtained composition wassubjected to injection molding to obtain test pieces, followed bymeasurements of bending strength, modulus of elasticity, impact strengthand thermal deformation temperature and also by a wear test. The resultsare shown in Table 8.

Example 47

The general procedure of Example 40 was repeated using 6-aminocaproicacid instead of the 11-aminoundecanoic acid thereby producing a glassfiber-reinforced polycarbonate resin composition. The resin compositionwas subjected to injection molding to provide test pieces, followed bymeasurements of bending strength, modulus of elasticity, impact strengthand thermal deformation temperature and also by a wear test. The resultsare shown in Table 8.

Example 48

The general procedure of Example 40 was repeated using p-aminobenzoicacid instead of the 11-aminoundecanoic acid thereby producing a glassfiber-reinforced polycarbonate resin composition. The resin compositionwas subjected to injection molding to provide test pieces, followed bymeasurements of bending strength, modulus of elasticity, impact strengthand thermal deformation temperature and also by a wear test. The resultsare shown in Table 8.

Example 49

0.5 kg of maleic anhydride-modified low density polyethylene (AdmerNB550), 0.05 kg of 11-aminoundecanoic acid, 4.5 kg of polycarbonate(MI=4 g/10 minutes) and 2.14 kg of glass fibers (having a fiber lengthof 3 mm and a diameter of the fiber of 9 μm and treated with anaminosilane) were sufficiently mixed in a Henschel mixer, followed bymelt kneading at 300° C. by use of a twin-screw extruder, therebyobtaining a glass fiber-reinforced polycarbonate resin compositioncomprised of 70 parts by weight of the polycarbonate resin compositionand 30 parts by weight of the glass fibers. The glass fiber-reinforcedpolycarbonate resin composition was dried at 120° C. for 8 hours,followed by subjecting to injection molding to provide test pieces. Thetest pieces were subjected to measurements of bending strength, modulusof elasticity, impact strength and thermal deformation temperature andalso to a wear test. The results are shown in Table 8.

Example 50

5 kg of maleic anhydride-modified linear low density polyethylene (AdmerNB550) and 50.5 g of 11-aminoundecanoic acid were sufficiently mixed ina Henschel mixer, followed by melt kneading at 260° C. by use of atwin-screw extruder. The resultant mixture was dried in vacuum at 80° C.for 12 hours, after which 0.5 kg of the mixture and 9.5 kg ofpolycarbonate (MI=4 g/10 minutes) were mixed in the Henschel mixer,followed by melt kneading at 300° C. by use of the twin-screw extruderto obtain a polycarbonate resin composition. The polycarbonate resincomposition was dried at 120° C. for 8 hours. 4.5 kg of thepolycarbonate resin composition and 0.5 kg of glass fibers (having afiber length of 3 mm and a diameter of the fiber of 9 μm and treatedwith an aminosilane) were sufficiently mixed by means of the Henschelmixer, followed by kneading at 260° C. by means of the twin-screwextruder to obtain a glass fiber-reinforced polycarbonate resincomposition comprised of 90 parts by weight of the polycarbonate resincomposition and 10 parts by weight of the glass fibers. The glassfiber-reinforced polycarbonate resin composition dried at 120° C. for 8hours, followed by injection molding to provide test pieces. The testpieces were subjected to measurements of bending strength, modulus ofelasticity, impact strength and thermal deformation temperature and alsoto a wear test. The results are shown in Table 8.

Comparative Example 27

The general procedure of Example 50 was repeated except that linear lowdensity polyethylene (Linirex AM0710) was used instead of the maleicanhydride-modified low density polyethylene (Admer NB550) and that11-aminoundecanoic acid was not added, thereby obtaining a glassfiber-containing composition. The thus obtained composition wassubjected to injection molding to obtain test pieces, followed bymeasurements of bending strength, modulus of elasticity, impact strengthand thermal deformation temperature and also by a wear test. The resultsare shown in Table 8.

Comparative Example 28

The general procedure of Example 38 was repeated except that 97 parts byweight of the polycarbonate resin composition and 3 parts by weight ofthe glass fibers were used, thereby obtaining a glass fiber-reinforcedpolycarbonate resin composition. The composition was subjected toinjection molding to obtain test pieces, followed by measurements ofbending strength, modulus of elasticity, impact strength and thermaldeformation temperature and also by a wear test. The results are shownin Table 8.

Comparative Example 29

The general procedure of Example 38 was repeated except that 50 parts byweight of the polycarbonate resin composition and 50 parts by weight ofthe glass fibers were used, thereby obtaining a glass fiber-reinforcedpolycarbonate resin composition. The composition was subjected toinjection molding to obtain test pieces, followed by measurements ofbending strength, modulus of elasticity, impact strength and thermaldeformation temperature and also by a wear test. The results are shownin Table 8.

                                      TABLE 8                                     __________________________________________________________________________                   Coeffi-                 Izod                                                  cient of        Flexural Strength/                                                                    Impact                                        Specific                                                                              Dy- HDT    Tensile                                                                            Flexural                                                                              Strength                                      Wear Loss                                                                             namic                                                                             (°C.,                                                                         Strength                                                                           Modulus (notched)                                     (×10.sup.-15 m.sup.3 /Nm)                                                       Friction                                                                          18.6 kgf/cm.sup.2)                                                                   (kgf/mm.sup.2)                                                                     (kgf/mm.sup.2)                                                                        (kgfcm/cm)                             __________________________________________________________________________    Ex. 38 5.2     0.23                                                                              142.3  12.92                                                                              19.23/842.31                                                                          15.6                                   39     4.2     0.19                                                                              140.2  12.13                                                                              18.92/819.82                                                                          17.5                                   40     2.8     0.15                                                                              142.1  11.42                                                                              18.05/725.01                                                                          19.6                                   41     4.5     0.19                                                                              140.2  12.25                                                                              18.92/819.83                                                                          17.6                                   42     5.0     0.20                                                                              140.0  12.09                                                                              18.97/821.35                                                                          17.1                                   43     4.2     0.i9                                                                              139.2  12.15                                                                              19.02/830.92                                                                          16.9                                   44     4.3     0.19                                                                              140.1  12.23                                                                              18.93/821.31                                                                          17.2                                   45     8.1     0.21                                                                              140.2  12.15                                                                              18.89/815.26                                                                          18.6                                   46     5.3     0.20                                                                              140.5  12.23                                                                              18.91/817.92                                                                          18.6                                   47     3.5     0.17                                                                              140.3  11.99                                                                              18.73/812.91                                                                          19.3                                   48     5.7     0.20                                                                              140.1  12.21                                                                              18.95/821.32                                                                          16.9                                   49     4.5     0.19                                                                              139.2  11.32                                                                              18.21/802.35                                                                          14.3                                   50     1.8     0.15                                                                              139.2  7.32 11.52/352.32                                                                          53.5                                   Com.Ex. 23                                                                           12.3    0.25                                                                              142.5  13.21                                                                              19.43/851.31                                                                          14.3                                   24     10.2    0.21                                                                              140.3  12.21                                                                              18.63/809.91                                                                          16.9                                   25     21.4    0.25                                                                              140.3  11.92                                                                              18.21/812.31                                                                          14.6                                   26     17.3    0.22                                                                              140.5  12.39                                                                              18.92/816.31                                                                          12.3                                   27     9.9     0.20                                                                              141.0  6.91 10.12/341.4                                                                           40.3                                   PC/PTFE/GF.sup.1                                                                     8.3     0.18                                                                              143.5  12.73                                                                              19.32/819.91                                                                          10.9                                   Com.Ex. 28                                                                           1.5     0.15                                                                              134.7  5.93  9.72/323.54                                                                          69.8                                   29     7.3     0.27                                                                              142.4  12.93                                                                              20.56/856.31                                                                          7.3                                    __________________________________________________________________________     .sup.1 A mixture of Lubriconp DL 4030 ® (7.0 kg) and glass fibers (3.     kg). The mixture was kneaded in a twinscrew extruder. The glass fiber was     the same as used in the Examples.                                        

As will be apparent from Table 8, the compositions of the inventionexhibit both good mechanical strength and heat resistance and goodsliding characteristics. In contrast, the compositions of thecomparative examples 23 to 27 are poorer in the wear property. Inaddition, the compositions of the examples have characteristicproperties similar to or greater than those of a knownpolycarbonate/fluorine resin (PTFE) sliding material set out as areference in the table.

EFFECT OF THE INVENTION

According to the invention, the PC-polyolefin resin compositions havinggood mechanical characteristics, heat resistance and surface propertiescan be obtained from readily available starting materials. Thesecompositions which have good properties as set out above are useful as amaterial for interior and exterior parts of automobiles and electric andelectronic appliances, housings, and machine parts such as gears, camsand the like.

According to the process of the invention, PC/polyolefin resincompositions having good mechanical strength, heat resistance andmiscibility can be readily obtained by a melt kneader.

According to the invention, the polycarbonate/polyethylene resincompositions can be provided as having good mechanical characteristics,heat resistance and sliding characteristics. By this, polycarbonatesliding parts can be provided as a substitute for the known PC/PTFEsliding material and as being more inexpensive, coupled with theadvantages that the problem of generation of harmful gases on combustionof PTFE can be solved and that such parts are good from the ecologicalstandpoint. The composition of the invention and moldings thereof haveutility as parts (such as gears, cams and the like) in the fields ofoffice automation devices, automobiles, and domestic appliances.

According to the invention, polycarbonate/polyolefin resin compositionhaving good mechanical characteristics, heat resistance and organicsolvent resistance can be provided. By this, polycarbonate-based partswhich are a substitute for known PC/polyester compositions and which aremore inexpensive and better in organic solvent resistance can beprovided. The composition of the invention and moldings thereof makinguse of the above characteristics are useful as parts of automobiles, OAdevices, domestic appliances and the like.

The glass fiber-reinforced polycarbonate resin compositions of theinvention are excellent in mechanical characteristics, heat resistanceand sliding characteristics. By this, there can be provided moreinexpensive polycarbonate-based sliding parts in place of known PC/PTFEsliding materials, so that the problem of the generation of harmfulgases on combustion of PTFE can be solved. The composition of theinvention and moldings obtained therefrom are useful mechanical parts inthe fields of OA devices, automobiles, domestic appliances and the likewhile making use of their characteristic properties.

We claim:
 1. A polycarbonate/polyolefin based resin compositionexhibiting an improved polycarbonate/polyolefin compatibility preparedby melt kneading(A) a polycarbonate resin; (B) a polyolefin resin; (C) apolyolefin resin that has been modified with at least one functionalgroup selected from the group consisting of epoxy, carboxyl, and an acidanhydride groups; and (D) a compound represented by the formula:

    HOOC--R--NH.sub.2

wherein R represents at least one member selected from the groupconsisting of an alkene group, an alkylidene group, and anoligomethylene group containing 5 or more carbon atoms, and phenylenegroup and naphthylene group optionally substituted with an alkyl group.2. A polycarbonate/polyolefin based resin composition exhibiting animproved polycarbonate/polyolefin compatibility according to claim 1wherein40 to 99% by weight of the component (A); greater than 0% and nogreater than 60% by weight of the component (B); 0.5 to 60% by weight ofthe component (C); and 0.05 to 5% by weight of the component (D) areused.
 3. A polycarbonate/polyolefin based resin composition exhibitingan improved polycarbonate/polyolefin compatibility according to claim 1wherein1 to 99% by weight of the component (A); greater than 0% and nogreater than 98% by weight of the component (B); 0.5 to 99% by weight ofthe component (C); and 0.05 to 5% by weight of the component (D) areused.
 4. A molded article produced by melt molding the resin compositionaccording to claim
 1. 5. A molded material having an improved solventresistance comprising the molded article according to claim
 4. 6. Amolded material having improved wear resistant properties comprising themolded article according to claim
 4. 7. A glass fiber-reinforced resincomposition comprising95 to 60% by weight of thepolycarbonate/polyolefin based resin composition according to claim 1;and 5 to 40% by weight of glass fibers.
 8. A molded article produced bymelt molding the glass fiber-reinforced resin composition according toclaim
 7. 9. A molded material having an improved solvent resistancecomprising the molded article according to claim
 8. 10. A moldedmaterial having improved wear resistant properties comprising the moldedarticle according to claim
 8. 11. A process for producing the resincomposition according to claim 1 comprising the step of melt kneadingacompatibilizer precursor prepared by reacting the polyolefin resin (C)and the compound (D) with the polycarbonate resin (A) and the polyolefinresin (B) simultaneously or sequentially in an arbitrary order.
 12. Aprocess for producing the resin composition according to claim 1comprising the step of melt kneading a compatibilizer prepared byreacting the polycarbonate resin (A), the polyolefin resin (C), and thecompound (D)with the polycarbonate resin (A) and the polyolefin resin(B) simultaneously or sequentially in an arbitrary order.
 13. A processfor producing the resin composition according to claim 1 comprising thesteps ofmelt kneading the polyolefin resin (B), an acid anhydride, andthe compound (D) represented by the formula:

    HOOC--R--NH.sub.2

wherein R represents at least one member selected from the groupconsisting of an alkene group, an alkylidene group, and anoligomethylene group containing 5 or more carbon atoms, and phenylenegroup and naphthylene group optionally substituted with an alkyl groupso that a part of the polyolefin resin (B) undergoes an in situconversion to form the modified polyolefin resin (C) through reaction ofthe polyolefin resin (B) and the acid anhydride; and continuing the meltkneading after adding the polycarbonate resin (A) simultaneously orsequentially in an arbitrary order.
 14. A process for producing theresin composition according to claim 1 comprising the steps ofmeltkneading the polycarbonate resin (A) and the compound (D) represented bythe formula:

    HOOC--R--NH.sub.2

wherein R represents at least one member selected from the groupconsisting of an alkene group, an alkylidene group, and anoligomethylene group containing 5 or more carbon atoms, and phenylenegroup and naphthylene group optionally substituted with an alkyl group;and continuing the melt kneading after adding the polyolefin resin (B),the polyolefin resin (C) that has been modified with at least onefunctional group selected from the group consisting of epoxy, carboxyl,and an acid anhydride groups, and a further addition of thepolycarbonate resin (C) in an arbitrary order.
 15. A resin compositionaccording to claim 1 whereinthe modified polyolefin resin (C) is thepolyolefin resin modified with at least one functional group selectedfrom the group consisting of carboxyl and an acid anhydride groups; andthe resin composition has been produced through reaction of the modifiedpolyolefin resin (C) with the compound (D) represented by the formula:

    HOOC--R--NH.sub.2

wherein R represents at least one member selected from the groupconsisting of an alkene group, an alkylidene group, and anoligomethylene group containing 5 or more carbon atoms, and phenylenegroup and naphthylene group optionally substituted with an alkyl group,whereby a linkage represented by formula (H): ##STR5## is produced. 16.A resin composition according to claim 1 whereinthe modified polyolefinresin (C) is the polyolefin resin modified with epoxy group; and theresin composition has been produced through reaction of the modifiedpolyolefin resin (C) with the compound (D) represented by the formula:

    HOOC--R--NH.sub.2

wherein R represents at least one member selected from the groupconsisting of an alkene group, an alkylidene group, and anoligomethylene group containing 5 or more carbon atoms, and phenylenegroup and naphthylene group optionally substituted with an alkyl group,whereby a linkage represented by formula (J): ##STR6## is produced. 17.A molded material having an improved solvent resistance comprising amolded article produced by melt molding the resin composition accordingto claim 1 wherein the polyolefin is dispersed in the polycarbonate inparticulate form, and the particulate polyolefin present in the regionfrom surface of the article to a depth of 20 μm has an average aspectratio (major axis/minor axis) of up to
 5. 18. A molded material havingimproved wear resistant properties comprising a molded article producedby melt molding the resin composition according to claim 1 wherein thepolyolefin is dispersed in the polycarbonate in particulate form, andthe particulate polyolefin present in the region from surface of thearticle to a depth of 20 μm has an average aspect ratio (majoraxis/minor axis) of up to 5.